Elena Baltacha, Anne Koethavong, Johanna Konta and Sam Murray all crashed out of the women's draw, while James Ward and Kyle Edmund exited.
Those defeats mean men's second seed Andy Murray and Britain's top two female players Laura Robson and Heather Watson will fly the flag for Britain from Tuesday.
Elena Baltacha insisted she had plans to quit tennis after she crashed out of Wimbledon in the first round after a 6-4 6-1 defeat to Italy’s Flavia Pennetta.
The former British number one missed eight months between the London 2012 Olympics - where she lost in the second round to former world number one Ana Ivanovic - and April with a foot injury.
She relied on a wildcard to make the All England Club after winning in Nottingham earlier this month, but was beaten by former top 10 player Pennetta, who is also coming back from a long-term injury.
Baltacha, the world number 167, saw her serve broken in the first game of the match as Pennetta raced into a commanding early lead.
The Ipswich-based player, urged on by a big crowd on Court Three in one of the opening matches at SW19, recovered briefly in the first set, only to lose it by a single break.
Pennetta, ranked one place higher than the Brit, went on to control the second set, losing just a single game in the process of wrapping up a very comfortable victory.
Baltacha, who was playing at Wimbledon for the 11th time in her career, could not find any rhythm on her serve as she slumped to a disappointing defeat on day one of the grass-court Grand Slam.
Last year, Baltacha hinted the Olympics could be her last event after a career that has too often been plagued by injuries.
But she insists the motivation of challenging rising British stars Robson and Watson, who are both in action on Tuesday, is still keeping her motivated.
"I actually retired after the Olympics and then, when I made the decision to continue, I decided it wasn't worth going through the pain of rehab after surgery unless I was going to give it a good shot," said Baltacha, who cracked the world's top 50 three summers ago.
"I'm nearly 30, so I've got a good few years left if I look after myself and stay away from injuries.
"I need to get my ranking back up, so I can get into the bigger events. It's probably too late for the US Open but my goal is to qualify automatically for the main draw at the Australian Open next year.
"I also want my British number one spot back and with Laura and Heather coming through, that's a great challenge to motivate me. With all the work that I'm putting in I honestly do believe I could be a contender to get back there.
"I'm disappointed to go out and I had patches where I played well but I was not consistent enough. My serve let me down and that is where I probably fell short."
Another former British number one, Londoner Anne Keothavong, completed a poor day for the home nations as she became the sixth Britain to be knocked out in the first round.
The 29-year-old world number 217 was beaten 6-4 6-0 by Spaniard Garbine Muguruza.
Elsewhere, Italy's Camila Giorgi put an end to Samantha Murray's hopes beating the British number seven 6-3 6-4 in double quick time.
And British number three Johanna Konta was also brushed aside by former world number one Jelena Jankovic.
Jankovic, a two-time semi-finalist at the All England Club, won the first set with ease but was made to fight for the second before claiming a decisive late break to win 6-2, 7-5.
In the men's draw, Kyle Edmund - who recorded his first ATP Tour win at Eastbourne in the lead up to the tournament - suffered a 6-2 6-2 6-4 defeat to 24th seed Jerzy Janowicz in his first-round match.
The Pole blasted 39 winners in securing the straight sets victory as Edmund struggled to get any momentum and failed to challenge his opponent on court three.
Edmund, 18, is increasingly viewed as having the long-term potential to follow the lead of world number two Andy Murray.
However, the youngest player in the men's singles draw was determined to accentuate the positive.
"I played okay but at this level I need to play better than that to win. He was a tough player to draw in the first round," admitted Edmund, who is ranked 442nd in the world.
"It was a tough day and I'm really disappointed but I can't lose sight of the long-term goal and I feel like I've improved so much in the last few weeks.
"The scoreline shows I got beat pretty comfortably but I served pretty well and, of course, there are areas that I need to improve on, there would be something pretty wrong if that wasn't the case.
"However, to be playing my first Wimbledon at 18 was a still a great feeling and I will never forget it.
"There is still lots of tennis for me here, I'm in the doubles and I'm also playing in the juniors."
British number two James Ward also lost, agonisingly missing out on an all-British second-round clash with Andy Murray after a 6-7(4) 6-4 7-6(11) 7-6(4) defeat to Taiwan's Lu Yen-Hsun.
The pair were almost inseparable with one break and three tie-breaks deciding the four setter, as the world number 75 triumphed against the man ranked outside the top 200.
That means Murray is the only British man left in the singles.