The absence of a bandgap in pristine graphene severely restricts its application, and there is high demand for other novel two-dimensional (2D) materials. PC₆ has recently emerged as a promising 2D material with a direct band gap and ultrahigh carrier mobility. In light of the remarkable properties of an intrinsic PC₆ monolayer, it would be intriguing to find out whether a doped PC₆ monolayer displays properties superior to the pure system. In this study, we have performed density functional theory calculations to understand the doping effects of both P-site and C-site substitution in PC₆ and, for the first time, we discovered doping-related impurity-level anomalies in this system. We successfully explained why no donor or acceptor defect states exist in the band structures of X_P–PC₆ (X = C, Ge, Sn, O, S, Se, or Te). In group-IV-substituted systems, these dopant states hybridize with host states near the Fermi level rather than act as acceptors, which is deemed to be a potential way to tune the mobility of PC₆. In the case of group-VI substitution, the underlying mechanism relating to doping anomalies arises from excess electrons occupying antibonding states.