Facing one of the more powerful top-orders in the league featuring Alyssa Healy, Shafali Verma, Ashleigh Gardner and Ellyse Perry, the Renegades delivered six overs of spin in the opening Powerplay on Sunday.
Left-armer Molineux and off-spinners Harmanpreet Kaur and Ella Hayward bowled two apiece, with the move paying off as they dismissed Verma (0), Gardner (7) and Healy (5) inside the first five overs to leave the Sixers reeling at 3-12.
Then, chasing 119 for victory, Molineux demoted herself to the middle-order and sent out English import Eve Jones to open the batting alongside India's Jemimah Rodrigues, with their 43-run first-wicket stand laying the foundation for a seven-wicket win.
Molineux later revealed the spin-heavy approach had not been premeditated, rather a call she made on the fly after bowling the first over of the game.
"We planned to bowl a bit of pace in the Powerplay, but after the first over we saw that (spin) could be effective so we just rolled with it," the first-year Renegades skipper said.
"Before we knew it, six overs had gone. It wasn't the plan going in, but that's the beauty of it, being able to adjust and adapt as we go."
The Renegades used just one over of fast bowling – in the 20th over – after the first 19 were delivered by a combination of the three spinners and medium pacers Courtney Webb and Carly Leeson.
It was only the second time in the competition's history no pace had been used in the first six overs; coincidentally the only other occasion was also between the Renegades and Sixers, back in WBBL|01 with Molineux also involved.
The 23-year-old said the Renegades would need to continue thinking outside the box as they try and cover the enormous loss of Australia leg-spinner Georgia Wareham, who ruptured her ACL in Wednesday's loss to the Adelaide Strikers.
"We're never going to be able to replace Wolfie (Wareham), who is one of the best leg-spinners in the world and even just her presence out there in the field and everything, we'll never replace her.
"But Ella came in and bowled her four overs beautifully and Harman was really good as per usual.
"I think we've all realised that we're going to have to step up in different ways to cover the big loss of Wolf but I suppose we're off to a good start on that front."
Molineux has been a fixture at the top of the order for the Renegades throughout her career but made a somewhat lacklustre start to the season with the bat, scoring 16 and 9.
She said the change had been made to better utilise the in-form Jones, and to get the most out of the Renegades' deep batting line-up, which also features the talents of Kaur, former Australia star Jess Duffin, and young guns Courtney Webb and Josie Dooley.
Uncapped English left-hander Jones hit 36no in the Renegades' loss to the Strikers, having earned her first WBBL contract after a breakout English domestic summer that saw her score 808 runs in the top order across three limited-overs competitions.
"Eve's hitting the ball really well. She opens the batting over in England and came off a really good (English summer), so we wanted to inject her into the game earlier," Molineux explained.
"One thing we took out of the game against the Strikers was that we've got a really long batting order and we need to be able to go from ball one.
"I'm happy to bat anywhere and Helmo (coach Simon Helmot) is a very experienced T20 coach who has juggled batting orders, and that's T20 cricket, there's a lot of juggling and adaptability from the players.
"We've got six or seven of us who are ready to go in (to bat) at any stage."
Meanwhile, Molineux, who replaced Amy Satterthwaite as Renegades captain this season, said she was relishing the chance to draw on the experience of India T20 skipper Kaur in what is her first opportunity to lead a senior side.
"To have the captain of India stand next to you at mid-off is pretty handy," she said.
"She's very open to giving honest feedback to all the girls and having her alongside me is really good, she's been able to calm me down a few times and she makes the game a little clearer."