Ninkovic's move to the Red and Black on a one-year deal last month after seven successful seasons with the Sky Blues was one of the biggest stories in the A-League Men off-season.
But Sydney's capture of Rodwell after his contract expired with the Wanderers will only add extra spice to this season's first derby on November 12.
The 31-year-old, capped three times by England, joined the Wanderers last year after a long career in England including stints with Premier League outfits Everton, Manchester City and Sunderland.
He made 14 ALM appearances for the Wanderers in his maiden campaign in Australia, scoring three goals.
"It is such a great feeling to join the most successful club in the country," Rodwell said in a statement.
"There is so much quality in the squad and combine that with the winning culture at this football club, this season has the potential to be one of the most exciting in our history.
"I still have so much to achieve here in Australia and I look forward to achieving that success with Sydney FC."
Sydney FC were left stunned by Ninkovic's defection after the veteran Serb rejected an offer from the Sky Blues which included a condition that the 37-year-old gained Australian citizenship to free up a visa spot.
Having suffered the fallout from that move, Sydney coach Steve Corica was delighted to lure Rodwell in the opposite direction.
"Jack's ability is unquestionable, he's played at the very highest level and he has adapted to the Australian conditions extremely well," Corica said.
"I expect him to get even better this season. He is still in his peak years as a footballer and can excel in various positions.
"We know we had significant competition to secure Jack and we are delighted to have a talent such as his on our books."
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