Wawrinka had caused the first major upset of the week when he battled Rafael Nadal throughout a thrilling quarter-final on Friday to send the seven-time Rome champion crashing out.
But despite a blistering start which saw Wawrinka race to a 3-0 lead in the opening set, the 30-year-old from Lausanne appeared to pay for his efforts late into the night at the Foro Italico.
Federer bounced back from losing the early break to break back twice on his way to sealing the first set 6-4.
Federer, bidding for his maiden title in Rome having lost three finals -- two to Nadal -- earned three break points in the third game of the second set and won the game when Wawrinka attempted a wild half-volley from a tight angle which he netted.
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Federer moved 3-1 up on his next service game and broke his fellow Swiss again for a 4-1 lead before wrapping up the set.
So far this year it's one apiece between Djokovic and Federer, the former winning their last final at Indian Wells to make amends for Federer's win in Dubai.
Career-wise, Federer holds the advantage with 20 wins to Djokovic's 18, although the Serb has shown glimpses of brilliance this week and a variety of shots that put all of his rivals in trouble.