After his return to Wallachia, he was elected deputy in the Extraordinary Public Assembly, the legislative forum established by the Imperial Russian overseers at the end of the Russo-Turkish War of 1828–1829, representing the Dolj County during the Pavel Kiseleff administration.

In the spring of 1844, the Wallachian government approved the request of the Russian engineer Alexander Trandafiloff, to be allowed to administer the country's mines (which were subject to private ownership).

[4] A clear separation between him and Romantic nationalists occurred when he ordered the refoundation of the Saint Sava College as a French-language school — based on his view that Romanian was incompatible with modernization.

Gheorghe Bibescu worked for better relations with Moldavia (the other Danubian Principality under Russian supervision), and, starting 1847, the two countries established a customs union, after an agreement with Mihail Sturdza, the Moldavian hospodar.

[2] Bibescu also convinced the Russian government to allow him to impose some taxes on those monasteries that had been dedicated to various Orthodox centers of worship outside the Danubian Principalities' territories (the ownership issue, stringent ever since the end of the Phanariote epoch, implied that church property eluded state intervention, channelling income towards places such as Mount Athos; it was to be settled through secularization under the rule of Alexandru Ioan Cuza).

On 11 June Gheorghe Bibescu accepted the proclamation; two days later he abdicated and left the country, leaving it to be ruled by a Provisoral Government which succumbed to Ottoman intervention in September.

The Brâncoveanu patrimony passed on to Zoe and Gheorghe Bibescu's son, Grégoire Bibesco-Bassaraba (the father of Anna de Noailles).