Melbourne Renegades 169 for 7 (Matthews 46, Hancock 4-20) beat Brisbane Heat 167 for 9 (Harris 65, Coyte 3-26) by two runs
Earlier, Matthews was due a match-winning score and she delivered with her best and most influential innings of the WBBL season, scoring 46 off 28 balls to help Renegades post 169 for 7.
Matthews took the early wicket of Georgia Redmayne and two slick catches before her heroics in the final over to restrict the Heat to 167 for 9.
With the bat, Matthews played strokes all around the ground. She was looking ominous in the closing overs until she was bowled by seamer Hancock, who finished with her career-best figures of 4 for 20.
The Renegades were 134 for 2 in the 16th over before Hancock and part-timer Harris pegged them back. Harris picked up 2 for 16 with her offspin.
The loss could be costly for the Heat who stay in third position on the WBBL table on 14 points, two behind leaders Perth Scorchers.