(CNN) -- Newly promoted Hercules pulled off the biggest win in their history by beating reigning champions Barcelona 2-0 at Camp Nou on Saturday.
Paraguayan forward Nelson Haedo Valdez scored twice to give Hercules - back in the top-flight after a 13-year absence - a huge win.
Despite Barcelona dominating proceedings debutant Valdez, signed from Borussia Dortmund, scored the first goal on 26 minutes and then another on 58 minutes.
Barcelona were unbeaten at home last season as they retained the league title.
Real Madrid beat Osasuna 1-0 at Santiago Bernabeu, after being held to a 0-0 draw in the first half.
After the re-start Ricardo Carvalho neatly slotted a goal home when Cristiano Ronaldo missed from ten yards out, although he maintained his composure to find Carvalho.
The win maintains Real Madrid's unbeaten start to the season.
In the German Bundesliga Bayer Leverkusen were held to a 2-2 draw by a 10-man Hanover on Saturday, leaving Leverkusen in mid-table and Hanover third behind leaders Hoffenheim.
Leverkusen's Michael Ballack was forced to limp off the field following a heavy tackle on his left knee.
The 33-year-old came off after just 30 minutes, suffering a further set-back on his return from injury.
Hanover were reduced to 10 men after just 36 minutes when Austrian defender Emanuel Pogatetz was shown a second yellow card and the subsequent red when he sent Leverkusen's Arturo Vidal flying with a dangerous tackle.
Hamburg drew 1-1 at home to Nuremberg which leaves them second in the table.
Stuttgart lost 2-1 at Freiburg to suffer their third defeat of the season.
Ex-England manager Steve McClaren is still looking for his first win of the season as his Wolfsburg side lost 2-0 at Dortmund whose Japanese midfielder Shinji Kagawa scored his first Bundesliga goal.
Hoffenheim continued their dream start to the season beating Schalke 2-0 on Friday to remain top of the table with three wins out of three.
In Serie A champions Inter Milan secured their first victory of the season with a 2-1 success at home to Udinese on Saturday.
Samuel Eto'o scored the winner after Antonio Floro Flores had cancelled out Lucio's early opener.