There was nothing to split Volkov and Ukrainian Artem Pryma with the rifle as the pair demonstrated their skills with 100 per cent accuracy.
But across the snow Volkov had the advantage and came home in 23:14.2 minutes to claim the title, 18.5 seconds ahead of Pryma.
And there was double joy for Russia as Sergey Klyachin completed the podium, taking bronze in 23:33.8 minutes.
Elsewhere, it was a Ukrainian one-two in the women’s 7.5km sprint with Olena Pidhrushna pipping compatriot Valj Semerenko to the European title.
It was her accuracy with the rifle that made all the difference for Pidhrushna as she avoided any penalties to come home in 20:33.0 minutes.
Semerenko however collected two time penalties, forcing her to settle for silver, 29.4 seconds back.
Poland’s Waronika Nowakowska-Ziemniak crossed the line in 20:58.3 minutes to collect bronze.