A delegation from the Organisation for Security and Co-operation in Europe is heading to Sloviansk in Ukraine to try to secure the release of military observers seized by pro-Russian gunmen.
The eight monitors and five others were captured in the eastern city on Friday.
The militia continues to occupy official buildings in a dozen eastern cities, defying the government in Kiev.
This comes as the US and EU are preparing new sanctions against Russia, accusing it of destabilising Ukraine.
US President Barack Obama said the Kremlin had "not lifted a finger" to implement last week's deal in Geneva aimed at easing the crisis.
He stressed it was important to take further steps to send "a message" to Moscow that its destabilising actions Ukraine must stop.
EU diplomats are expected to meet on Monday to discuss fresh sanctions against Russia. The G7 group of economic powers has also agreed to intensify sanctions.
The Kremlin denies supporting the militia in eastern Ukraine.
'Fundamental option'The OSCE team was sent to Sloviansk after receiving the organisation's mandate to start the negotiation, an OSCE source told the BBC.
The source declined to say how many negotiators were heading to the flashpoint eastern town and whether they would be engaged in direct talks with militia leaders.
Meanwhile, Sloviansk's self-declared mayor Vyacheslav Ponomaryov told Reuters: "When the representatives of the OSCE come, we will talk to them about it (the detained observers)."
Asked about the possibility of exchanging the monitors for militia members held by the Kiev government, he replied: "It's the fundamental option."
Russia, an OSCE member, earlier pledged that it would "take all possible steps" to secure the release of the observers from Germany, Denmark, Poland, Sweden and the Czech Republic.
Meanwhile, Kiev accused the militia of using the Europeans as a "human shield".
In a separate development on Sunday, pro-Russian gunmen said they had captured three Ukrainian security services members overnight in eastern Ukraine.
Kiev later confirmed that an unspecified number of its officers had been seized.
Troop movement fearsThe West is accusing Moscow of leading a secessionist revolt in eastern Ukraine after it annexed Crimea last month. Russia strongly denies the claim.
On Saturday, US Secretary of State John Kerry "expressed continued concern that Russia's provocative troop movements on Ukraine's border, its support for separatists and its inflammatory rhetoric are undermining stability, security and unity in Ukraine", his office said.
Mr Kerry also "urged Russian support without preconditions for the efforts of the OSCE and the government of Ukraine to liberate the... inspectors and their Ukrainian guides," the statement added.
For his part, Russian Foreign Minister Sergei Lavrov said Ukraine must end military operations in the east of the country as part of urgent measures to defuse the crisis.
Ukrainian troops have carried out a number of raids to try to regain control of official buildings.
The crisis began when protesters toppled pro-Russian President Viktor Yanukovych in February and has since plunged East-West relations to their lowest point since the Cold War.
Russia has tens of thousands of troops deployed along its side of the border with Ukraine and has said it will act if its interests are threatened.
On Saturday, the G7 praised Ukraine for acting with restraint in dealing with the "armed bands" that had occupied government buildings.
But the group, which comprises the US, UK, Germany, Japan, France, Canada and Italy, condemned Russia's "increasingly concerning rhetoric and ongoing threatening military manoeuvres."
The G7 said it was committed to intensifying sanctions on Russia, ahead of Ukrainian presidential elections next month.
The US and EU already have asset freezes and travel bans in place targeting a number of Russian individuals and firms accused of playing a part in the annexation of Crimea.
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