Messi struck a brilliant opener after just 12 minutes to put Barca on track, and then played a key role as Pedro Rodriguez made it 2-0 soon after as the Catalan giants built a 3-1 aggregate lead.
Messi, who was a constant menace, added a third on the hour mark to take his tally to eight goals in the last four games before Bojan Krkic completed the romp late on as Barca became Spain's only representative to make it into the last eight.
Real Madrid, whose Bernabeu Stadium will stage this year's final, and Sevilla were both dumped out in the last week while Atletico Madrid bade farewell to the competition in the group stages.
Barca coach Pep Guardiola opted to start Thierry Henry as centre-forward instead of Zlatan Ibrahimovic and the Frenchman was the home side's biggest threat early on, bringing a save out of Jens Lehmann in the second minute and then shooting wide not long after.
It was Messi who took centre stage after that, though.
Fresh from his stunning treble in Sunday's 3-0 win over Valencia - his second hat-trick in 2010 already - the Argentinian broke the deadlock with a superb finish.
Yaya Toure fed the reigning FIFA World Player of the Year near the halfway line and the diminutive playmaker was allowed to venture unchallenged to the edge of the Stuttgart area before unleashing an unstoppable shot that flew into the top corner.
Messi then turned provider 10 minutes later as Barca doubled their advantage.
His brilliant pass inside the Stuttgart right-back was latched onto by Toure, and his first-time pass inside was slotted home by Pedro.
Those two early strikes put Barca in total control and with Stuttgart creating little to trouble Victor Valdes and his defence, Guardiola's sextuple winners went into the half-time interval knowing only a huge reversal of fortunes in the second half would deny them a place in the next round.
The script did not change at all though, with Messi again featuring heavily.
He set up Toure for a low shot that fizzed just wide in the 55th minute before then extending Barca's lead five minutes later.
Pedro's pass back to the edge of area was cleverly flicked into Messi's path by Dani Alves, and the 22-year-old spun Timo Gebhart and drilled another left-footed shot past Lehmann from 20 yards out.
That was Messi's fourth Champions League goal of the season and took his tally to 29 in all competitions
It ended any doubt about which team would be part of Friday's draw, and the only question was how many more goals Barca would add against a Stuttgart side who have taken just one point from their last two Bundesliga games and need a tremendous end to the season if they are to get back into the Champions League again.
Messi had two chances to net his hat-trick, being denied by a superb Lehmann save and then dinking the ball wide with only the veteran goalkeeper to beat, while Andres Iniesta also went close.
Barca did manage to get one more goal though as substitutes Ibrahimovic and Bojan combined in the 89th minute for the latter to slide home a low shot from outside the area.
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