Xabier Azkargorta's men and the visiting Sport Boys were separated by just one point prior to their fixture in La Paz.
However, the difference was damning at the Estadio Hernando Siles - as a William Ferreira hat-trick in addition to Jaime Arrascaite's opener gave Bolivar a commanding lead at the interval.
Juanmi Callejon added a fifth after 71 minutes, as Bolivar cruised to the three points.
Bolivar sit in sixth spot after snapping their three-match losing run, seven points behind third-placed The Strongest - who occupy the closest continental spot.
'Will Cristiano Ronaldo and Neymar extend their contracts in Saudi Arabia? We play a facilitating job, but it’s down to the players and the clubs to decide' Saudi Pro League chief reveals how talks will work for out-of-contract duo
Nations League: Who are the ITV commentators and pundits for England vs Republic of Ireland?
