EU foreign affairs chief Federica Mogherini will make her first official visit to Russia this month, with relations strained to breaking point by the Ukraine conflict and the war in Syria.
She will also visit China and India next week, her office said in a statement on Wednesday.
Most attention is likely to focus on her trip to Moscow on April 24, with ties in deep freeze over its support for pro-Russian rebels fighting an insurgency in eastern Ukraine and its 2014 annexation of Crimea.
Adding to tensions, the European Union is pushing for a political solution in Syria without President Bashar al-Assad, Moscow's long-time ally.
The announcement of the trip comes just as US Secretary of State Rex Tillerson is in Moscow for talks with Foreign Minister Sergei Lavrov to confront Russia over its support for the Assad regime.
Mogherini will also meet Lavrov to "discuss the most pressing foreign policy issues, in particular the conflict in Syria", the statement from her office said.
They will also discuss the situation in Libya, the Middle East peace process, Iran, Afghanistan and Ukraine, as well as EU-Russia ties.
Mogherini took office in 2014 with a reputation of being sympathetic to Russia when she was Italian foreign minister and said repeatedly she wanted to visit Moscow.
She tried to stabilise relations with Moscow, arguing that Russia was a huge neighbour that the EU had to learn to live with, but the deepening Ukraine crisis prevented any accommodation.
Mogherini will visit China on April 19 to chair the EU-China Strategic Dialogue with top Chinese foreign policy official Yang Jiechi in preparation for an EU-China summit later in Brussels, a statement said.
They will discuss global challenges, such as climate change, as well as regional and security issues, it said.
In India on April 21, Mogherini will hold similar talks with Indian Foreign Minister Sushma Swaraj.
Mogherini has led efforts to give the EU a high profile voice on the international stage as a major security player, with the bloc looking to a post-Brexit future.