The other last-four tie sees Juventus - in their first semi-final since 2003 - face Carlo Ancelotti's Real Madrid, the defending champions.
The first legs will be played on 5 and 6 May, with the return matches a week later.
In the Europa League, holders Sevilla face Fiorentina, while Rafael Benitez's Napoli are up against Ukraine's Dnipro.
Bayern boss Guardiola won 13 trophies as a manager - including the Champions League in 2009 and 2011 - during four years at Barcelona.
He has reached the Champions League semi-finals in each of his six seasons as a manager, four with Barca and now two with Bayern.
The draw leaves open the possibility of a Barcelona v Real Madrid European Cup final, something which has never happened before. The arch-rivals are also battling it out for the Spanish league title this season.
Real Madrid reached the last four by beating city rivals Atletico - in a repeat of last season's final - thanks to Javier Hernandez's late goal.
Bayern Munich thrashed Porto 6-1 at home to overturn a first-leg deficit and progress 7-4 on aggregate.
Things were more straightforward for Barcelona, who beat Paris St-Germain 5-1 overall, and Juventus, who beat Monaco 1-0 over two legs.
This season's final will be played at Berlin's Olympic Stadium on Saturday, 6 June.
The Europa League draw leaves the possibility of an all-Serie A final. There have been four all-Italian Uefa Cup finals, but none since the tournament was rebranded in 2009.
The first legs of the semi-finals will be played on Thursday, 7 May with the return matches a week later.
The final is in Warsaw's National Stadium on Wednesday, 27 May.
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