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Villarreal will compete in the Europa League this season after Uefa confirmed Real Mallorca's place in the competition had been withdrawn.
The governing body of football in Europe announced on Thursday they had denied Mallorca entry to the tournament due to financial irregularities.
That means fellow Spaniards Villarreal will take their place in the league instead of their cash-stricken counterparts.
Mallorca are set to appeal the decision but failure would mean Juan Carlos Garrido's side would take part in the second-tier event.
Uefa sad in a statement on the Villarreal official website, read: "In relation to the decision taken by the Committee of control and discipline on July 22, we want to announce that RCD Mallorca have not been admitted into the UEFA Europa League 2010-2011.
"In consequence, as established by paragraph 2.12b of the competition rules, we want to inform via this note that Villarreal (having reached seventh place in the Spanish league), subject to the fulfilment of all the relevant conditions, will be admitted to the UEFA Europa League 2010-2011 in place of RCD Mallorca."
Mallorca applied to go into voluntary administration in May after amassing debts thought to be in the region 70million euros (£60m).
But they reacted angrily to the announcement and are preparing to the challenge the decision.
A club statement read: "This decision is seriously harmful to the club's administration process as there were a series of revenues expected that would have allowed payments to creditors."
The relevant ruling states that any club not admitted will be replaced by another of the same federation and that if the sanctioned club are not the cup winners, the team that replaces them must be the one that was best positioned in the league standings.
That means Villarreal - who finished seventh in Primera Division last time out - are due to take part, but Mallorca coach Michael Laudrup is hopeful the ban will be overturned.
The former Real Madrid and Barcelona star said: "I'm optimistic, I can see no logical reason why this should happen. I think the club will appeal. I do not think we will stay out."
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Real Mallorca president Jaume Cladera has resigned from his post with the Primera Division club.
Real Madrid's fading title hopes were dealt another blow with defeat at Malaga as Barcelona won at Real Valladolid.
Mallorca got their first win in 15 games in all competitions as they came from behind to beat Real Betis 2-1.
Karim Benzema has warned Barcelona that Real Madrid are not going to relinquish their La Liga title without a fight.
Athletic Bilbao and Malaga won in the Primera Liga on Saturday, while Getafe salvaged a point against Osasuna.