Bolotov was elected at an assembly session Sunday. The session also approved a temporary constitution for the people of Luhansk.
Along with electing the leader, Vassily Nikitin has been elected as the prime minister.
“My first steps at the post of the Republic’s Prime Minister will be to form a government. I shall announce specific candidacies later on,” Nikitin said.
The two east Ukrainian regions of Luhansk and Donetsk held referendums May 11 to declare their independence from Kiev.
Some 96 percent of voters in Luhansk had voted in favour of independence, while 89 percent of voters in neighbouring Donetsk backed breaking away from Ukraine.
The West and Ukraine have deemed the referendums as illegal.
The self-proclaimed People’s Republic of Donetsk last week elected Alexander Borodai as prime minister and co-chairman Denis Pushlin was elected as the parliament speaker.