 Gheorghe Bibescu was married to Zoe Brâncoveanu, the last of the Brâncoveanu family, therefore inheriting all the titles and wealth.The marriage was unsuccessful, as Zoe became mentally ill. Bibescu entered into a conflict with the Orthodox Church, as he wanted to divorce Zoe.He eventually managed to obtain the divorce in 1845 and in September of the same year, he married Maria Văcărescu, in Focşani.