Single-atom adsorbents (SAAs) featuring maximized atom utilization and uniform isolated adsorption sites have aroused extensive research interest in recent years as a novel class of adsorption materials research. Nevertheless, it is still challenging to gain a fundamental understanding of the complicated behaviors of SAAs for adsorbing thiophenic compounds (THs). Herein, this work systematically investigated the mechanisms of adsorption desulfurization (ADS) over a single group IIIA metal atom (Ga, In, and Tl) anchored on hexagonal boron nitride nanosheets (BNNSs) via density functional theory (DFT) calculations. First, all the possible doping sites have been considered and their stabilities have been evaluated by the doped energy. DFT calculations reveal that metal atoms prefer to substitute B atoms on BNNSs rather than N atoms. Additionally, SAAs all exhibit considerably enhanced adsorption capacity for THs primarily by the sulfur-metal (S-M) bond with π-π interactions maintained. Among them, In-atom-based SAAs would be adequate to provide the highest adsorption energy (In_cen_B, -40.1 kcal mol-1). Furthermore, from the perspective of adsorption energy, the SAAs show superior selectivity to THs than aromatic compounds due to the newly formed S-M bond. We hope that our work will manifest the design and application of SAAs in the field of ADS and shed light on a new strategy for fabricating SAAs based on BNNSs.