The 35-year-old played for the Victory previously for two seasons, from 2013 to 2015, with spells between at Boston Breakers and Washington Spirit in the U.S. National Women's Soccer League.
"To be back with this club again and to be playing again is incredible," De Vanna told ESPN in an exclusive interview. "It just shows the type of journey football can lead you on, especially when I was thinking about hanging up the boots six months ago."
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Given the mass exodus of Australian superstars such as Sam Kerr, Caitlin Foord and Steph Catley to Europe during the offseason, De Vanna is now one of the biggest names in this season's Australian domestic competition.
The experienced striker's decision to join the Jeff Hopkins-coached Victory will boost the club's chances of wrestling the W-League title from reigning champions and arch-rivals Melbourne City.
"There's a great mix of players in the squad" De Vanna said. "I'm enjoying being back in the team environment -- it's like falling in love with the game again.
"We've had a tough preseason and the intensity and standards have been really high. It's great to see everyone working hard -- players now know that the door is open to being a Matilda.
"We can't wait to play our friendlies next week. I can't wait to finally play some football again, but mostly to see some [teammates] step up now."
De Vanna last played competitively for Italian Serie A club Fiorentina in their 2019-20 season, which was postponed in March and ultimately curtailed due to COVID-19.
She made 14 regular-season appearances for Fiorentina, scoring five goals as they finished second in the league.
"I loved playing there," De Vanna said of her spell with Fiorentina.
"Out of all my years as a player, I don't think I've enjoyed myself at a club more. I love what they represented: Passion and family.
"It's a special place, a special time for me. It's very sad the way it had to end, but with the pandemic sweeping Europe the league really had no choice."
Already Australia's record goal-scorer for both women's and men's teams, De Vanna is a single international appearance away from equalling Cheryl Salisbury's record of 151 Matildas caps. Two more appearances will place De Vanna in the rarified air of holding a nation's goal-scoring and appearance records simultaneously.
The achievement could have been reached already, but for her exclusion from Australia's friendlies with Chile last November, as former coach Ante Milicic looked to the future with a youthful squad that saw De Vanna's potential milestone put on hold.
De Vanna is adamant that her international career isn't over, however, and she's out to impress the new Matildas coach, Tony Gustavsson, as he starts his reign.
"I'm not done wearing green and gold," she told ESPN. "I'll always be available for my country, like I have done for the past 20 years.
"Hopefully, I can prove that by playing my heart out for Melbourne Victory this coming season.
"As long as I play, I'll never stop wanting to represent Australia."
Melbourne Victory start their season away to Western Sydney Wanderers at Bankwest Stadium on Dec. 27.