The report, which received a large majority of votes in plenary, also requests the European council to be prepared for the third phase - economic sanctions - which should be applied immediately.
Speaking on the issue, ALDE group leader Guy Verhofstadt said, "What is happening now in the eastern part of Ukraine is totally unacceptable especially in the light of recent events in Crimea.
"What is happening now in the eastern part of Ukraine is totally unacceptable" - Guy Verhofstadt
"If dialogue with Russia today in Geneva does not make Russia re-evaluate their strategy in Ukraine then the EU will have no other choice but to slap extra sanctions on those responsible to increase the pressure on Russia to relent."
Hans van Baalen, the group's spokesman on Ukraine, was also critical of Moscow, saying, "It seems that Putin has learned nothing from his illegal annexation of the Crimea and continues to pursue the same policy with the same means of deceptions and propaganda.
"The Geneva talks that start today will be a good opportunity to test Russia's real intentions and whether they are genuinely open to constructive dialogue or not."
Meanwhile Elmar Brok, chair of parliament's foreign affairs committee and his group and committee colleague José Ignacio Salafranca Sánchez-Neyra, issued a joint statement, saying, "It is beyond doubt that Russia is continuing to stoke tensions in eastern Ukraine by supporting and leading separatists and militias.
"It is necessary to make clear to Russia that the international community will not allow an outright breach of international law”, they continued.
"Russia must withdraw its troops from the Ukrainian border, lift the decree allowing for a military invasion of Ukraine, and issue clear orders to separatists and militias in Ukraine to immediately withdraw and refrain from all violence."
They added, "Ukraine is a sovereign country and must be allowed to hold free and fair elections on 25 May, without outside interference. The OSCE and the EU have to send election observers to make sure international democratic rules are respected."
Hannes Swoboda, S&D group chair, said, "The fact that all four powers - the EU, US, Ukraine and Russia - are meeting for direct talks is an achievement in itself. There have been many threats in the last weeks but none have helped resolve the crisis in Ukraine.
"The fact that all four powers - the EU, US, Ukraine and Russia - are meeting for direct talks is an achievement in itself" - Hannes Swoboda
"Instead of verbal and military aggression, dialogue must now be the approach of choice," he argued.
"While respecting Ukraine's independence and sovereignty, we must ensure Russia has no legitimate grounds for concern over Russian-speaking citizens in Ukraine.
"The best defence against unjustified Russian aggression is a policy of inclusion, particularly ahead of the presidential elections on 25 May.
"The European Union is by definition not interventionist. The strength of the European Union lies in mediation and facilitating dialogue. This is our task in the case of Ukraine and Russia, too.
"The EU continues to fully support the visa liberalisation process that has begun with Ukraine and remains committed to a clear European perspective for Ukraine, Moldova and Georgia," said the Austrian deputy.
Greens/EFA co-president Rebecca Harms was less positive about the talks, saying, "Expectations are low for the Geneva talks but the stakes could not be higher for Ukraine.
"Everything possible should be done to stabilise the situation and enable the Ukrainian government to fully exercise its powers," she urged.
"Everything possible should be done to stabilise the situation" - Rebecca Harms
"All efforts should be made to prevent Ukraine becoming a dysfunctional state, along the lines of Bosnia, in which one community can use its veto power to paralyse the country.
"As a first step towards de-escalation, we call for an immediate withdrawal of Russian troops from the border with Ukraine.
"If today's talks are unsuccessful, EU governments need to urgently convene an extraordinary council with a view to preparing a third phase of sanctions against Russia.
"MEPs have today also called for the strengthening of the OSCE mission in Ukraine. This is essential if it is to play a meaningful role in monitoring the situation as regards human rights, atypical military activity and provocative actions in eastern Ukraine," she concluded.