Abstract Substitutional doping of 2D transition metal dichalcogenides (TMDCs) has been recognized as a promising strategy to tune their optoelectronic properties for a wide array of applications. However, controllable doping of TMDCs remains a challenging issue due to the natural doping of these materials. Here, the controllable growth of Ti‐doped MoS 2 monolayers is demonstrated via the chemical vapor transport method, and the atomic embedded structure is confirmed by scanning transmission electron microscope with a probe corrector measurements. Furthermore, the grown Ti‐doped MoS 2 monolayer exhibits giant photoluminescence (PL), 85‐fold stronger than a pristine MoS 2 monolayer prepared by the same method. The giant PL enhancement is attributed to dopant‐induced O‐Ti‐S units and improved interaction between the monolayer and the mica substrate, increasing the photoluminescence quantum yield and facilitating radiation recombination. The successful growth of Ti‐doped MoS 2 monolayer and the improvement of its optical and electrical properties by Ti doping may provide a promising method to engineer the optoelectronic properties of 2D TMDCs materials.