Two-dimensional (2D) monoelemental bismuth (Bi) crystal, one of the pnictogens (group VA), has recently attracted increasing interest because of its intriguing characteristics. Here, uniformly sized 2D Bi quantum dots (BiQDs) with an average diameter (thickness) of 4.9 ± 1.0 nm (2.6 ± 0.7 nm) were fabricated through a facile liquid-phase exfoliation (LPE) method, and the corresponding photoresponse was evaluated using photoelectrochemical (PEC) measurements. The as-fabricated BiQDs-based photodetector not only exhibits an appropriate capacity for self-driven broadband photoresponse but also shows high-performance photoresponse under low bias potentials ranging from UV to visible light in association with long-term stability of the ON/OFF switching behavior. In terms of these findings, it is further anticipated that the resultant BiQDs possess promising potential in UV–visible photodetection as well as in liquid optoelectronics. Our work may open a new avenue for delivering high-quality monoelemental pnictogen QDs from their bulk counterparts, thereby expanding interest in 2D monoelemental materials.