The Aussies were left to rue a 12-25 conversion rate from the free-throw line while they shot just 47% from the field as well in another frustrating offensive performance.
They still had a chance to take the victory though, trailing by a point with the last possession of the game.
Out of a time-out, the Rollers were able to find captain Brad Ness (ten points) on the wing but his bank shot just rimmed out and the Aussies were unable to claim the rebound as time expired.
The final term was a see-sawing affair but after trailing by two points at three-quarter time, the Rollers' defensive intensity picked up to hold Brazil scoreless through the first two minutes of the fourth period.
Adam Deans (four points, three rebounds) and Joshua Allison combined on the scoreboard to give Australia the lead before Shaun Norris connected on an incredible three-point play as he was knocked over on the shot.
That sent the Rollers into the bonus but they struggled to make the most of their opportunities from the free-throw line and at the other end of the floor, Marcos Candido Sanchez (17 points, 16 assists) nailed two from the charity stripe in the final 30 seconds in what would prove to be game-winning shots.
Australia's offence was flowing at the start of the contest, scoring 11 points inside the first four minutes and while Brazil were able to stay in touch through the first period, a Brett Stibners triple gave the Rollers a three-point lead at quarter-time.
The Rollers kept their noses in front through the second term thanks to their three-point shooting with Stibners (13 points, three assists) adding another long range bomb before Tristan Knowles (15 points, nine assists) got involved as well.
They would go on to shoot 5-6 from deep as a team but their problems began to grow at the other end of the floor with Leandro de Miranda (24 points) proving a handful.
His bigger frame enabled him to create room in the paint while also showing a quality touch from all around the court and he was the first player in double-figure scoring with 17 points by half-time.
Jannik Blair (two points, three steals), as he had done throughout the tournament, brought the defensive pressure to start the third term, forcing a turnover and finding Bill Latham (six points, four rebounds) streaming down the floor for an easy lay-up.
That sparked an 8-4 run for the Aussies and gave them a little breathing room but Erik Da Silva (13 points) and Candido Sanchez responded once more for Brazil, turning the margin around to take their own two-point margin into the final change and that momentum swing proved decisive.
The full box score can be found here.
The loss marks a disappointing finish to the Rio 2016 campaign for Australia who started the tournament with three victories before losing three of their next four.
Norris and Knowles were still two of the most productive and exciting players at the Paralympics though while a bevy of young talent including debutants Allison, Deans, Tom O'Neill-Thorne, Shawn Russell and Matt McShane will hold the team in good stead as they prepare themselves for a comeback in Tokyo.