The 24-year-old informed the Magpies she would be crossing to the Harbour City after five seasons in the black and white which she played 47 games, kicking 37 goals.
According to AFL Media's Riley Beveridge, the four expansion clubs - Sydney, Essendon, Hawthorn, and Port Adelaide have been given first use of poaching players from other clubs when the Sign and Trade period begins next Wednesday.
After a winless campaign, Sydney can access up to five players during the sign-and-trade period without having to make a trade and they can offer long-term contracts to players from other clubs.
The Pies conceded on Wednesday morning that any hopes of a backflip had been dashed, thanking Molloy for her service by way of an official statement.
“Over the past five years, Chloe has been a great ambassador for our Club and the wider AFLW competition and it's been great to watch her grow and develop as both a player and person over the course of that time.
“Not only has Chloe demonstrated outstanding talent on the field, but she has also made strong contributions off field including as an opposition analyst during her time on the sidelines with a Lisfranc injury in 2019.
“In this situation, we understand that she was interested in seeking an opportunity interstate in pursuit of a new lifestyle.
“Whilst we're disappointed Chloe won't be a part of the continued growth of our program, we are confident in the depth and talent of our playing list to ensure continued improvement in the 2023 season and beyond.”
“On behalf of everyone at Collingwood, we would like to thank Chloe for all she has brought to our Club and we wish her all the best for this next chapter of her career.”
Molloy also took to social media on Wednesday morning, tweeting that joining Collingwood "was a dream that I still can't believe came true".
(1/4) Being drafted to Collingwood in 2017 was a dream that I still can’t believe came true. To have a black and white guernsey to call my own, and create my own legacy in #2, is something I cherish beyond words. The club is part of my identity and always will be….
— Chloe Molloy (@chloemollloy) February 22, 2023
A number of Collingwood players including veterans Stephanie Chiocci and Jaimee Lambert have received substantial interest from St Kilda whilst Hawthorn is targeting experienced midfielder Mikala Cann.
With Molloy's departure, Collingwood could potentially receive compensation with the League yet to come to a decision as to whether all 18 clubs will have access to draft picks in 2024.
As for the other 14 clubs, the sign-and-trade period will run from Friday, March 10 to Monday, March 20.