Wozniacki looked to be cruising to victory after taking the first set with ease and then going up 5-4 in the second and serving for the match.
She took advantage of Mertens' erratic play, with the world No.37 making 34 unforced errors.
But two nervy double-faults handed Mertens the break back - and invitation back into the contest.
The Belgian smelt a choke in the offing, reeling off seven straight points to go up 6-5.
Mertens had two set points but couldn't close it out herself, with Wozniacki belting a forehand to force a tiebreak.
With the pressure on both players, Wozniacki's consistency and big-match experience proved key with the former world No.1 dominating the tiebreak.
Before the match, Wozniacki admitted she was still haunted by her 2011 Open semi-final loss to Li Na when she blew a match point before losing in three sets.
This win should go some way to atone for that disappointment.
Wozniacki will move to world No.1 if current queen Halep loses her semi-final later on Thursday.
If they clash in the final, the winner will leave Melbourne with the top ranking as well as the trophy and $4 million winner's purse.