Amialiusik, 26, timed her challenge to perfection in scorching heat, hovering behind her rivals before stepping on the gas 50 metres from the finish of the 120.7 km course.
Poland's Katarzyna Niewiadoma took silver and Dutchwoman Anna van der Breggen bronze with the trio credited with the same time of three hours, 20 minutes and 36 seconds.
The Netherlands had already qualified for next year's Olympics but unlike other Rio-bound leading nations sent a strong squad to Baku, despite the absence of injured Olympic gold medallist and 12-time world champion Marianne Vos.
Ellen van Dijk took the individual time trial title on Thursday but another medal eluded her as she finished 18 seconds behind the podium places in fourth having been unable to reel in the trio in the latter stages.
Van der Breggen appeared set to spark more Dutch celebrations when she led into the final straight but was a sitting target for Amialiusik who dug deep in the shadow of the finish line.
Amialiusik, third in the team time trial at last year's world championships having finished 15th in the road race at the 2012 London Olympics, said the hot conditions were no problem for her.
"I am accustomed to riding in the heat. In terms of tactics, it was difficult, the Dutch came with an Olympic team, with strong racers. There was six of them and they were the dominating team. The most important thing was to remain calm and have faith in yourself.”
Amiakiusik compared the course, which included sections of cobbles in the old town of the capital, to a "Belgian classic".
She also said victory would not have been possible without the efforts of her team mates.
"Tatsiana (Sharakova) helped me a lot because she protected me from the Dutch athletes and without her I could not have won," she said.
"They (Netherlands) were very strong but you don't have to be strong, you just have to be with your team and have teamwork."
(Additional reporting by Parniyan Zemaryalai; editing by Toby Davis)
Share
