The Russian pair, who were second after the rhythm dance portion of the event, produced a stunning performance in the free dance to leapfrog French pair and five-time defending European champions Gabriella Papadakis and Guillaume Cizeron and claim the gold medal.
Sinitsina and Katsalapov won the title with a combined score of 220.42, narrowly defeating Papadakis and Cizeron, who finished with a score of 220.28.
Another Russian pair, Alexandra Stepanova and Ivan Bukin took the final place on the podium with a score of 211.29.
Previously, Sinitsina and Katsalapov won silver at the World Figure Skating Championships in 2019.