Svitolina, 19, joined Bojana Jovanovski and Vera Zvonareva as a Baku Cup champion after taking out the third edition of the event last year.
The Ukrainian - seeded seventh at the time - accounted for Israeli opponent Shahar Peer 6-4 6-4 for her maiden WTA title.
World number 35 Svitolina - the second seed this time around - heads to the hard courts in Azerbaijan on the back of a quarter-final berth at the Istanbul Cup.
She disposed of Montenegrin Danka Kovinic and Switzerland's Stefanie Voegele before suffering a shock defeat to Croatian qualifier Ana Konjuh in the last eight.
Top seed Sorana Cirstea will be hoping for a second WTA title, though she is set to arrive in Azerbaijan with a lack of competitive action.
Cirstea's only triumph can back in 2008 when she prevailed in three sets against Sabine Lisicki in the now defunct Tashkent Open.
But the Romanian world number 29 has not spent much time on court in recent times, with her first-round exit at Wimbledon -a three-set loss to American youngster Victoria Duval - her most recent appearance.
One player with form on her side, albeit on clay, is German and two-time WTA winner Mona Barthel.
Barthel - the eighth and final seed in Baku - went deep at the Swedish Open in Bastad as she made it past the quarters.
Slovakian Magdalena Rybarikova (third), Japan's Kurumi Nara (fourth), 2012 champion and Serbian Jovanovski (fifth), Austrian Yvonne Meusburger (sixth) and Great Britain's Heather Watson are the other seeds making up the draw in Baku.