Herein, we have investigated the tunability of the photoluminescence (PL) of the monolayer MoS2 (1L-MoS2) by decorating it with WS2 quantum dots (WS2 QD). The direct bandgap 1L-MoS2 and WS2 QDs are grown by chemical vapor deposition and liquid exfoliation methods, respectively. The room temperature PL spectrum of bare 1L-MoS2 is systematically quenched with its decoration with WS2 QDs at different concentrations. A decrease in the work function of 1L-MoS2 with the decoration of WS2 QDs was established from the Kelvin probe force microscopy analysis. A detailed quantitative analysis using the four-energy level model involving coupled charge transfer was employed to explain the redshift and the systematic decrease in the intensity of the PL peak in 1L-MoS2/WS2 QD heterostructure. The modulation of the PL in the heterostructure is attributed to the increase in the formation of negative trions through the charge transfer from WS2 QD to the 1L-MoS2 and thus making the 1L-MoS2 heavily n-type doped, with increase in the electron density by ~1.5 × 1013 cm-2. This study establishes the contribution of defects in the coupled charge transfer dynamics in 1L-MoS2, and it lays out a convenient strategy to manipulate the optical and electrical properties of 1L-MoS2 for various optoelectronic applications.