Former world number one Williams began the encounter brightly and went on to break Kirilenko's serve at the second time of asking.
She then went on to hold her remaining service games before taking a one-set lead courtesy of a 6-3 success.
Kirilenko responded positively in the second set, forcing Williams into a tie-breaker. There looked to be very little to split the pair until Russia's Kirilenko broke to win the breaker 7-5 and force a deciding set.
Kirilenko failed to build upon that triumph as she surrendered her service game early in the third set. Williams, on the other hand, continued to dominate with a series powerful forehand strokes.
She eventually won the set and the match 6-3 6-7 6-2.