Pietersen and skipper Alastair Cook had safely negotiated the opening hour, but two balls after first drinks Mitchell Johnson struck when Pietersen injudiciously hooked a bouncer straight to backward square leg.
Substitute fielder Chris Sabburg, on for paceman Ryan Harris, claimed the catch to a huge roar from the home crowd.
It was an inopportune choice of shot by Pietersen with the tourists needing to bat for two days to prevent Australia from taking a 1-0 lead in the five-Test series.
England will be banking on Cook to reprise his 10-1/2 hour stonewalling of Australia from the corresponding Test of the 2010-11 Ashes series in Brisbane.
Three years ago captain Cook frustrated Australian efforts with his unconquered 235 as England killed off the match with their 517 for one in the second innings after trailing the home side by 221 runs on the first innings.
Australia have not lost a Test at the Gabba since 1988 and England will have to create Ashes history to win, with their previous highest winning fourth innings score at 332 for seven in Melbourne in 1928.
The world record for the highest successful run chase is the West Indies' 418 for seven against Australia in Antigua in 2003, while the highest winning chase at the Gabba is Australia's 236 for seven against the West Indies in 1951.
England had a wretched start to their marathon salvage operation when Michael Carberry was bowled by Harris through his legs for a duck in the fifth over, and Jonathan Trott pulled Johnson straight to Nathan Lyon at deep square leg for nine.
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