The Organisation for Security and Co-operation in Europe will "deploy a special monitoring mission of international observers to Ukraine", a resolution passed by the OSCE's 57 member states said.
The mission will initially be of 100 observers and "as necessary and according to the situation ... May expand by a total of up to 400 additional members", it said.
Russia's ambassador to the OSCE, Andrei Kelin, said in Vienna after the decision the fact that the mission will not be deployed in Crimea was in line with "geopolitical realities".
Having blocked at OSCE headquarters such a mission for the past week, he said that it "might be a first and important step to de-escalate tension in this area".
According to the text, the aim is to "contribute throughout the country and in co-operation with ... Relevant actors in the international community (such as the United Nations and the Council of Europe), to reduce tensions and fostering peace, stability and security".
The OSCE's current chairperson and Swiss Foreign Minister Didier Burkhalter said advance teams would be sent "within 24 hours".
The mission's mandate is six months but can be extended if Ukraine requests so and OSCE members states approve.
"Throughout the country, the mission will gather information and report on the security situation as well as establish and report facts regarding incidents, including those concerning alleged violations of fundamental OSCE principles and commitments," Burkhalter said in a statement.
Russia this week annexed mainly Russian-speaking Crimea after a referendum in the Black Sea peninsula slammed by Western countries as illegal.
Welcoming the OSCE decision, German Foreign Minister Frank-Walter Steinmeier said before heading to Ukraine tomorrow that this was "not the end of the crisis but a step that will help us in our de-escalation efforts".
"The situation in Ukraine remains unstable, dangerous too. Therefore the observers must begin their work as soon as possible," Steinmeier said.
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