Neal-Bullen joined the Crows from Melbourne and is among four deputies to captain Jordan Dawson.
The 29-year-old Neal-Bullen, Ben Keays, Darcy Fogarty and Reilly O'Brien have all been named vice-captains.
Neal-Bullen, a premiership player with the Demons in 2021, has made an instant impact on coaches and teammates during his first pre-season with the Crows.
"We had a focus in the off-season to add more leadership and experience to our team, and we were fully aware of his ability to impact in this space," Adelaide coach Matthew Nicks said in a statement on Tuesday.
"He has embraced the club and his new teammates from day one and he will be a great addition to our leadership group."
Nicks said re-appointing Dawson, who joined the Crows from Sydney at the end of the 2021 season, was an "an obvious choice".
"He sets the tone, leads by example and his on-field direction had been outstanding over the past two years," the coach said.
"He's super-competitive, driven and brings others with him, so we look forward to that continuing.
"Ben and Reilly have also been part of the leadership group for a number of years now and demonstrate an elite level of professionalism, combined with a genuine care for others.
"Darcy stepped up into a leadership role for the first time last year, was our leading goalkicker and finished top-five in our best-and-fairest.
"He has built strong connections within the playing group and committed his future to the club until 2031, which is a real positive for us."Â
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