The 39-year-old steps up from his assistant role to replace the departing Mykhailo Fomenko following a disappointing Euro 2016 campaign, which saw defeats in all three group games, including against Northern Ireland in Lyon.
A statement on the Football Federation of Ukraine website said Shevchenko’s appointment was on a two-year deal, with the possibility of extension.
“The executive committee of the Football Federation of Ukraine unanimously supported the candidature of Andriy Shevchenko,” the statement read.
“The coaching staff will include Italians Mauro Tassotti and Andrea Maldera, known for work in the structure of (AC) Milan, and Spaniard Raul Riancho, who from 2014 to 2016 worked as assistant coach at Dynamo Kiev.”
Shevchenko started his playing career at Dynamo Kiev, before joining Italian giants AC Milan in 1999, winning the 2003 Champions League and the Ballon d’Or in 2004.
The striker joined Chelsea for £30million in 2006, before a loan spell back at Milan and then Kiev, retiring in the summer of 2012 after Ukraine had co-hosted the European Championship.
After a brief stint in politics, Shevchenko – Ukraine’s record scorer with 48 goals in 111 games – joined the national team coaching staff ahead of Euro 2016 as assistant to Fomenko.