Second round

The draw for the second round took place on 20 December. It was divided in two geographical groups, with first division teams seeded to play away against teams from lower divisions.

Matches were played over one leg on 2nd and 3rd January 2001, and the results were as follows:

Only eight first division clubs survived through to the third round draw which takes place on Friday 5th January. Five were eliminated in the first round, including Real Madrid at Toledo, and seven more fell in the second round which was played over one leg at the ground of the lower division side. The shock of the day was the elimination of Valencia by minnows Gaudix, who are currently lying at the bottom of the Southern regional group of the second division B. They surprised an under-strength Valencia taking a 3-0 lead before half time, but the European sub-champions came back with two goals in the last five minutes, including a controversial penalty in injury time by Zahovic. After a further 30 minutes extra time the game went to a penalty shoot out, and Angulo finally shot wide after both teams had scored all five in the first round of spot kicks. Tenerife made it a clean sweep of the surviving Champions League teams by eliminating Deportivo La Coruña 3-2. The game was level at 1-1 with ten minutes to go before Simutenkov got a couple, with Pandiani getting one back in injury time.

Five other first division teams were also eliminated, including Las Palmas who were reduced to eight men before being beaten 2-1 by second division B team Torrelavega, who knocked out Alavés in the first round. The home side took the lead through Chili on the half hour mark from a free kick after Olías was sent off, but Eloy squared the tie at one apiece in the second half. With ten minutes to go referee Pérez Lasa awarded a penalty to the home side, sending off keeper Cicovic for the foul and then Vinny Samways, presumably for an audible obscenity. Last year's runners up Atlético Madrid, now in the second division, knocked out first division Osasuna with a couple of second half goals from Correa, and Leganés cruised to a 2-0 victory against a disappointing Numancia. Valladolid goalkeeper Bizzarri saved a second half penalty against Extremadura to take the game to extra time, but his side still lost 2-1, and Villarreal saw second division B side Granada claw back a goal in the last minute to take the game to extra time and penalties. Two saves by the Granada keeper in the shoot out were enough to put them through.

Three goals in the second half gave Barcelona victory at Ceuta, the Spanish enclave in North Africa. Fans were hanging off the floodlights as the second division B side held on for the first hour until the introduction of Guardiola turned things around. With Rivaldo and Overmars resting, Alfonso took his opportunity, scoring the first two goals. Barcelona's neighbours Espanyol, defending champions in this competition ,went through 0-2 against Levante, but only after their keeper Argensó saved a penalty in the first half. No joy for another two of last round's giant killers Beasain and Toledo, losing 0-3 to Zaragoza and 0-1 to Rayo Vallecano respectively, although Rayo's goal came from a Toledo player in the first half.

Two very late goals by Carlos and Finidi gave Mallorca a flattering 0-3 scoreline at Xerez, and Celta were forced to extra time before Edu scored one and made another for Karpin to give them a 1-3 victory. Compostela's Biscay had levelled scores in the last minute of normal time, but got himself sent off for a second yellow card after taking off his shirt in celebration, leaving his side with ten men. Racing Santander had no trouble beating Badajoz 0-4, with the home side even missing a late penalty, and Athletic Bilbao came back from behind against 2B side San Sebastian de los Reyes to win 1-2. In the only second division clash, Murcia beat Jaén in the penalty shoot out after nine spot kicks each.