The exploitation of highly efficient and cost-effective selective adsorbents for adsorptive desulfurization (ADS) remains a challenge. Fortunately, single-atom adsorbents (SAAs) characterized by maximized atom utilization and atomically dispersed adsorption sites have great potential to solve this problem as an emerging class of adsorption materials. Herein, aiming at improving the efficiency of ADS performance via the economical and feasible strategy, the desirable SAAs have been fabricated by uniformly anchoring aluminum (Al) atoms on hexagonal boron nitride nanofibers (BNNF) via an in situ pyrolysis method. Remarkably, Al-BN-1.0 exhibited a superior adsorption capacity of 46.1 mg S/g adsorbent for dibenzothiophene, with a 45% increase in adsorption capacity compared to the pristine BNNF. Additionally, it demonstrated excellent adsorption of other thiophene sulfides. Moreover, the ADS mechanisms have been investigated through special adsorption experiments combined with density functional theory (DFT) calculations. It was demonstrated that the superior ADS performance and selectivity of Al-BN-1.0 originate from the sulfur-aluminum (S-Al) and π-π interactions cooperating synergistically. This work would cast light on a novel fabrication strategy for the SAAs based on the two-dimensional material with a tunable metal site configurations and densities for varied selective adsorption and separation.