A novel photocatalytic urea synthesis strategy is proposed for the preparation of ureas from amines and carbon disulfide (CS2), with Rhodamine B utilized as the photocatalyst. Conducted under mild reaction conditions, this method does not require the use of extra oxidants and efficiently yields a series of (un)symmetrical ureas and benzimidazolones under blue light irradiation. Furthermore, control experiments with oxygen-18 labeling have been conducted, which demonstrate that the carbonyl oxygen in the urea products is predominantly derived from the oxygen in the air through an oxidative desulfurization process.