Foreign Minister José Manual García Margallo also stressed the need for dialogue and cooperation during talks with Russian Foreign Minister Sergei Lavrov in Madrid.
Spain's top diplomat recognized Russia's key role in international affairs and said he hoped "fruitful dialogue" to end the crisis in Ukraine.
He also reiterated Spain's backing of EU sanctions, agreed upon during an emergency meeting in Brussels on Wednesday. "We want the situation to calm down and we want a de-escalation," said Margallo.
"Russia and the EU have to come to an understanding, they are very important players in international life," he concluded.
The comments came after Russia said on Wednesday it has no authority over pro-Moscow forces that have taken de-facto control of Ukraine's majority-Russian Crimean Peninsula.
A day after US President Barack Obama said Russia was "not fooling anybody" over its role in Ukraine, Russian Foreign Minister Sergei Lavrov insisted the armed troops in Crimea were not taking orders from the Kremlin.
Lavrov called for all sides to respect the letter of the law, treaties, and the Ukrainian constitution so as to allow calm to be restored.
"If they are the self-defence forces created by the inhabitants of Crimea, we have no authority over them," Lavrov told a news conference in Madrid after his with Spanish Foreign Minister Margallo.
"They do not receive our orders," said the top Russian diplomat.
The Russian foreign minister, who left Madrid after the news conference for Paris to meet with US Secretary of State John Kerry, said Moscow would not allow bloodshed to erupt in Ukraine.
"We will not allow bloodshed. We will not allow attempts against the lives and wellbeing of those who live in Ukraine and Russian citizens who live in Ukraine," he said.
Ukrainian troops remain blocked inside their barracks in Crimea in the gravest stand-off between the West and Russia since the end of the Cold War.
Lavrov recalled a 1994 US-Russia-British security agreement in which the three sides agreed to respect Ukraine's independence and to refrain from the threat or use of force or economic coercion.
The Russian minister accused the United States of issuing sanctions on Ukraine, after Washington revoked the visas of officials allegedly linked to the violence, and the European Union of having "threatened" Ukraine over its decision not to sign a treaty with the bloc.
"I would ask everyone to remember that this is a very complex problem," Lavrov added.
"To calm the situation we have to rely on the letter of the law and not create a situation or a sensation that one can violate absolutely all the treaties including the constitution of Ukraine," he added.
Lavrov's meeting with Kerry will be their first since Ukraine's Moscow-backed president Viktor Yanukovych was ousted after three months of pro-European Union protests which left nearly 100 dead.
Spain's foreign minister said Ukraine's troubles began with Yanukovych's decision not to sign a political and trade deal with the European Union.
Margallo said the European treaty had been "erroneously" presented as an alternative that excluded a Ukrainian Customs Union with Russia.
"They should not be considered as exclusive options, as incompatible options. They should be seen as two pillars for advancing towards an agreement of free association between Russia and the European Union to create a free trade zone from Lisbon to Vladivostok," the Spanish minister said.