For former world No 1 and two-time Grand Slam victor Azarenka, it was her first final in three years, after giving birth and being embroiled in a custody battle for her son.
With the win, Azarenka has stormed into the summit showdown of a WTA event for the first time since making a return to the tennis court following the birth of her son Leo in December 2016.
However, she gained a lot of momentum in Monterrey, starting with wins over Misaki Doi, Stefanie Voegele, and Sachia Vickery.
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"I'm very pleased with how I played today", she said in an on-court interview on a warm night in northern Mexico.
"It was an important match and to see how I can do under pressure against a top player", she said.
The game was tied at 4-all, but Kerber was beginning to lose her sting and Azarenka became more confident breaking her and then soon she'd captured the set 6-4.
Garbine Muguruza defended her Monterrey Open title after Victoria Azarenka was forced to retire with a leg injury.
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Keys won the next point but twice had backhand errors to allow Wozniacki to pull within 6-5.
The fifth seed broke Martic twice in the second set to claim the win and maintain her record of never having lost a set to Martic in six meetings.
"It's been a long time since I made this long run here", said the Dane who won the SC tournament in 2011.
The former French Open and Wimbledon champion broke the pained Belarusian three times in the first set and again in the fourth game of the second. "I think I did a pretty good job to close it out".
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