The 52-year-old former defender, a key member of the Bulgaria team that reached the 1994 World Cup semi-finals, signed a contract until the end of the 2018 World Cup qualifiers.
Hubchev, who was Bulgaria's assistant coach between 2003 and 2005, will have to deal with a hugely demanding and impatient fan base.
He is Bulgaria's 10th national coach since Plamen Markov's sacking after Euro 2004 - the last time the team appeared at the finals of a major tournament.
Hubchev, who played for Eintracht Frankfurt and Hamburg SV in Germany and coached several Bulgarian top-flight clubs, will take charge of the national team for the first time on Oct. 7 when Bulgaria visit France in a 2018 World Cup Group A qualifier.