Molloy, whose move was confirmed on Wednesday, has signed with the Swans ahead of their second season in the women's competition.
The 24-year-old won the AFLW Rising Star award, a club best-and-fairest and two All-Australian jumpers during a successful stint with the Magpies.
"I've had six seasons in the AFLW and if I'm being honest, I never pictured myself in the red and white, but have to admit it does look good," Molloy said in a club statement.
"The way I was evolving as a player and as a person, it led me to Sydney, and I was really drawn to the Swans.
"I'm eternally grateful for Collingwood and how they turned me into a person that I'm proud to be."
Sydney coach Scott Gowans already has a strong relationship with Molloy from his time as an assistant at Collingwood.
"Chloe has proven to be amongst the top echelon of players in the AFLW competition in recent years and she will set a great example on and off the field for our club," Gowans said.
"One thing I enjoy most about Chloe is her work ethic, and her desire to compete and improve will have a profound impact on those around her."
The AFLW priority sign and trade period runs until March 8 and is open to the four newest clubs in the competition - Sydney, Essendon, Hawthorn and Port Adelaide.
Following that, the AFLW sign and trade period for the remaining 14 clubs runs from March 10 to 20.
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