In 1840 he was a prosecutor in the trial of the participants in the Mitică Filipescu plot, and later on he was Wallachia's Minister of Internal Affairs.

Afterwards, on 11 June 1848, when the Wallachian revolution started in Bucharest, Nicolae Golescu was a Minister of Internal Affairs for the Provisional Government.

The following week, he and Ana Ipătescu took initiative in rallying civilians in defense of the revolutionary power, as it was threatened by conservative plot (June 19).

In 1866, after joining the alliance of Liberals and Conservatives against Cuza's unsanctioned personal regime, he was for a short time one of the regents.

He was then Foreign Minister and a member of Ion C. Brătianu's Liberal Party, formed during the rule of Carol I.