Defect engineering of2D semiconducting transition metal dichalcogenides (TMDCs) has been demonstrated to be a promising way to tune both their bandgaps and carrier concentrations. Moreover, controlled introduction of defects in the source/drain access regions of a TMDC FET can boost its performance by decreasing the contact resistance at the metallTMDC interface [1]. While chemical functionalization offers a facile route towards defect engineering in 2D TMDCs, several chemically-treated TMDCs have not been fully understood at the molecular level. In this study, chemical sulfur treatment (ST) utilizing ammonium sulfide [(NH4)2S] solution is shown to enhance the p-type behavior in 2D WSe2 via introduction of acceptor defect states near its valence band edge (VBE), with the results verified using detailed scanning tunneling microscopy (STM)/spectroscopy (STS) studies, field-effect transistor (FET) measurements and theoretical density-of-states (DOS) calculations.