Here, Football.co.uk takes a look at five of their previous encounters.
Barcelona 1 Inter 0 Champions League, April 28, 2010
With Mourinho claiming his first win over Guardiola eight days earlier, the Italian side produced a defensive masterclass at the Nou Camp to seal an aggregate win, sparking wild celebrations from the Portuguese tactician at the final whistle
Thiago Motta was sent off after just 26 minutes but despite Gerard Pique's late goal, Inter held on to advance to the Champions League final which they subsequently won 2-0 against Bayern Munich
Barcelona 5 Real Madrid 0 LaLiga, November 29, 2010
In his first Clasico Mourinho suffered the heaviest defeat of his managerial career as Guardiola's men outclassed their rivals in every sense of the word
A David Villa brace, and goals from Xavi, Pedro and Jeffren sealed victory before Sergio Ramos' late dismissal rubbed more salt into the wounds.
Barcelona 3 Real Madrid 2 Spanish Super Cup, August 17, 2011
The second leg of their fiery Spanish Super Cup clash at the Nou Camp was best remembered for one of the most ill-tempered touchline melees in recent years
After their 2-2 draw three days earlier, goals from Andres Iniesta and Lionel Messi put the Catalans ahead twice in the game but Cristiano Ronaldo replied before Karim Benzema looked to have forced extra-time
Messi sealed a 5-4 aggregate win, however, with a volley two minutes from time before wild scenes saw Marcelo, Mesut Ozil and Villa all shown red cards as both sets of players and benches faced off
Mourinho then appeared to poke Barcelona assistant Tito Vilanova in the eye during the brawl
Barcelona 2 Real Madrid 2 Copa del Rey, January 25, 2012
The Catalans held off a strong Real charge to advance to the Copa del Rey final and leave Mourinho's side with only one win in their last 10 games against Barca
Pedro and Dani Alves looked to have put the tie out of reach in the first half but two goals in the space of four minutes through Ronaldo and Benzema set up a tense finish
Barcelona were able to hold on as their fans unveiled a mock advert that said: "Wanted: a worthy rival for a decent clasico
Ask here for details."
Barcelona 1 Real Madrid 2 LaLiga, April 21, 2012
'The Special One' rallied his troops when it mattered as Real finally secured victory over Barca, handing their rivals their first defeat at home in 55 games and earning a first win in the Clasico in five years
Ronaldo's winner saw Madrid move closer to their first LaLiga title since 2008
Sami Khedira had put the visitors in front before Alexis Sanchez levelled
Mourinho's side would go on to claim the title while Guardiola quit as Barca boss at the end of the season
Source : PA
Source: PA