Barca is 15 points adrift of Carlo Ancelotti's runaway LaLiga leader and has lost its past five games against Madrid in all competitions.
That streak has only been bettered once in meetings between the two rivals, with Los Blancos enjoying a seven-game winning run between April 1962 and February 1965.
However, since Xavi's arrival, Barca has climbed to third in the league, taking 34 points from 15 games in LaLiga, a record only beaten by Madrid in that period (39 points).
The Blaugrana head coach wants his side to call upon that recent form to right the wrongs of previous clashes with Ancelotti's team.
"I don't know if there was an inferiority complex, I wasn't in charge," Xavi said during a pre-match news conference when asked about Barca's recent Clasico record.
"It's a great opportunity to change history, and a win would greatly support what we're working on.
"I don't know if we arrive with more self-esteem than previous years, but we do have good dynamics and enthusiasm against a rival who are in great form.
"We have to be brave, trying to impose our ideas, but also calm because there will be moments of everything. From my experience, I can transmit calm; it is just another chance for three points, and we have to try to enjoy the occasion.
"Luckily, I have very good memories of great victories and great feelings having played very good games there [at the Santiago Bernabeu] and also winning, something that does not always happen."
Barca will be boosted by the confirmed absence of Madrid talisman Karim Benzema, who limped off towards the end of last week's 3-0 win over Real Mallorca.
The France international tops LaLiga's scoring charts this season with 22 goals, finding the net on average once every 93.6 minutes, and he also leads the way with 11 assists.
Xavi acknowledged Benzema's injury will be a blow to Madrid's chances, with the striker having scored in two of his past three meetings with Barca in all competitions, as many as he had in his previous 16 appearances against the Blaugrana.
"Benzema is one of the best strikers in the world, it's a bad loss, but for us our approach doesn't change," Xavi said. "I suppose that for them it can change something.
"How to replace Benzema is a question for Ancelotti, but he has options."
Even with victory in the Spanish capital, Xavi acknowledges Barca's chances of a title push remain incredibly slim.
Asked if there was greater pressure to win against Madrid to spark a late surge, he responded: "I don't see it that way, the pressure is the same.
"If we win, we would be closer to the first objective, which is to be in the Champions League next season. But I see winning the league as complicated. We would be within 12 points, with a game in hand, it is complicated.
"If we win, I do see a parallel with 2004 [a 2-1 win at Madrid]. That victory didn't help us win the league either, but it did strengthen us and change the dynamic, as could happen now."