Fellow Brits Lisa Whybourn and Samantha Murray both bowed out in straight sets after their matches were moved indoors on a rain-affected day at the Nottingham Tennis Centre.
Baltacha meets Barbora Zahlavova Strycova in the quarter-finals on Friday after the Czech edged past Murray 7-5(6) 7-5.
The only thing that slowed Baltacha down in the all-British showdown on Thursday was the rain, having taken command of proceedings in the first set before heavy showers moved in.
It was five hours, and two false starts later, before the the Aegon Team GB Fed Cup star finished the job.
Baltacha was wary of more than just Webley-Smith’s serving power and tenacity during the match as she grappled with the on-again, off-again nature of play for the first time since returning from surgery.
“I had to stay strong in my head because we were on and off three times,” Baltacha said.
“That is where experience really counts, and I feel I've got a good art for dealing with it.
"It was pretty valuable situation to be in because I’ve not been put through that since I’ve come back. Now with Wimbledon approaching, where you know there is going to be rain, it proved to be good practice.”
It was the first time Baltacha has scored successive wins after eight months out of the game.
“It is a good feeling,” she said.
“Last week I couldn’t piece my game together at all and now to do it back-to-back like that is quite good and hopefully I can do it for a third day.”
Aegon Trophy champion and second seed Petra Martic set up a quarter-final date with seventh seed Tadeja Majeric of Slovenia after brushing Yurika Sema aside 6-3 6-0.
Meanwhile in the men’s draw, Ruben Bemelmans stormed into semi-final meeting with South Africa’s Rik De Voest on Friday after beating Dzmitry Zhyrmont 6-2 6-3 in less than an hour.
Earlier in the day, the Belgian picked up where the rain forced him to finish against newly crowned Aegon Trophy champion Matthew Ebden on Wednesday.
The 25-year-old had was already a set and 4-1 up in the second when play resumed at 11:50 BST, and it took only minutes for Bemelmans to seal victory 7-6(2) 6-3.
The world No. 141, who made it through to the quarter-finals of the Aegon Trophy in Nottingham last week, had to sit idle for more than six hours for his quarter-final to start, but it failed to disrupt his stunning run of form.
“The wait didn’t bother me - I didn’t get tired, lazy or have heavy legs. I was comfortable as soon as I stepped on court,” Bemelmans said.
“I’m playing really well at the moment, feeling the ball well. This week the courts are bit more worn out and quicker because of the weather, the rain, and I’d say that it is suiting my game a little better.”
In the other semi-final, Samdev Devvarman faces Steve Johnson after coming from a set behind to beat another American Donald Young in two hours and 20 minutes on Thursday night.
Young missed his chance to set up an all-American affair, serving for the match at 5-4 in the second set. Devvarman frustrated the former world No. 38, taking the set in a tiebreak before sealing his place in the last four.
Men’s singles – Second Round
R Bemelmans (BEL) d  M Ebden (AUS) 7-6(2) 6-3
 J Sock (USA) d S Devvarman (IND) 1-6 7-6(5) 6-3
Men’s Singles – Quarter-finals
R Bemelmans (BEL) d D Zhyrmont (BLR) 6-2 6-3
S Devvarman (IND) v Donald Young (USA) 3-6 7-6(4) 6-4
S Johnson (USA) d  I Marchenko 7-6(4) 6-0
R D Voest (RSA)  G Soeda (JPN) 3-6 6-1 6-3
Women’s singles – Second Round
E Baltacha (GBR) d [Q] E Webley-Smith (GBR) 6-1 6-3
[Q] M Miyamura (JPN) d  J Glushko (ISR) 6-4 6-3
 N Burnett (ITA) d AS Mestach (BEL) 7-6(2) 6-2
M Brengle (USA) d A Vrljic (CRO) 6-4 6-2
S Dubois (CAN) d [WC] L Whybourn (GBR) 6-2 6-1
 T Majeric (SLOV) d A Mitu (ROU) 6-4 6-4
 B Zahlavova Strycova (CZE) d [WC] S Murray (GBR) 7-6(6) 7-5
 P Martic d Y Sema (JPN) 6-3 6-0