In the absence of Vos, who pulled out of the inaugural continental games following a spate of injuries, van Dijk beat Ukraine's Ganna Solovei and Dutch compatriot Annemiek van Vleuten to claim her nation's first gold medal of the games.
"It is the first European Games and that is quite special. This was a race I have been preparing for, for weeks," 28-year-old van Dijk told reporters at Bilgah Beach.
"I have been training at high altitude. I wanted to be very strong in this period and that worked out great.
"Before the start I felt good. I was confident I could do this. But then the time trial is very hard to see how strong the competition is especially as there are not a lot of time trials during the season.
"The only thing you can really do is focus on your own time trial."
There are a further three gold medals available in road cycling with the men's time trial later on Thursday before the women's and men's road races on June 20 and 21.
The European Games runs till June 28.
(Editing by Sudipto Ganguly)
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