Tuning the optical and electrical properties of two-dimensional (2D) hexagonal boron nitride (hBN) is critical for its successful application in optoelectronics. Herein, we report a new methodology to significantly enhance the optoelectronic properties of hBN monolayers by substitutionally doping with sulfur (S) on a molten Au substrate using chemical vapor deposition. The S atoms are more geometrically and energetically favorable to be doped in the N sites than in the B sites of hBN, and the S 3p orbitals hybridize with the B 2p orbitals, forming a new conduction band edge that narrows its band gap. The band edge positions change with the doping concentration of S atoms. The conductivity increases up to 1.5 times and enhances the optoelectronic properties, compared to pristine hBN. A photodetector made of a 2D S-doped hBN film shows an extended wavelength response from 260 to 280 nm and a 50 times increase in its photocurrent and responsivity with light illumination at 280 nm. These enhancements are mainly due to the improved light absorption and increased electrical conductivity through doping with sulfur. This S-doped hBN monolayer film can be used in the next-generation electronics, optoelectronics, and spintronics.