With the new Ferrari F2003-GA car finally ready, Schumacher secured his second pole in a row and third of the season with a time of 1 minute, 17.762 seconds - the best mark of the one-hour session.
"We always felt we had a chance of pole as we know this car is faster than the old one and at this track, the car's performance is very important," Schumacher said.
"How does this car differ from the old one? It's faster! You always aim to make a car faster and more neutral and the team has worked on each detail of the package."
Despite earning his 53rd career pole, the five-time champion from Germany warned that there are still adjustments ahead.
"This weekend is the first time I have driven the new car at this track and so it was not easy to find the right direction of setup, but today's result shows we seem to have got it right," he said. "As usual with a new car, we have more work to do."
Schumacher has dominated the Circuit de Catalunya. Saturday's pole is his fourth straight and sixth overall at the track. He has won here four times, came in second twice and third on three occasions.
With Ferrari's new engine taking its time to appear, Schumacher started the season slow, but his win at San Marino last week put him third in the standings.
Barrichello clocked a time of 1:18.020, giving the Brazilian his third front row start of the season.
"The car worked very well, as we managed to improve its balance," he said. "But it was not a great lap for me. Being first and second on the grid is a very good start for the new car."
"This is a special day for me since - as I had hoped -I was able to place my car in the second row of the start grid at my home Grand prix," he said. "I think that both Jarno and myself are in the position to fight a good race (Sunday) and bring some more valuable points to the team."
The talented 21-year-old has earned points in all four races this season, with top finishes of third in Brazil and Malaysia.
Britain's Jenson Button will start Sunday's race fifth in his BAR Honda, followed by Olivier Panis of France in a Toyota, Germany's Ralf Schumacher's Williams and David Coulthard of Scotland in a McLaren-Mercedes.
Series leader Kimi Raikkonen of Finland, who owns a 13-point advantage over his McLaren teammate in the standings, will be forced to start from the back of the grid after going onto the gravel in the final sector of his flying lap.
Sunday's race, the fifth of 16 in the series, is 65 laps around the 2.936-mile track for a total of 190.838 miles.