In order to avoid the impurity phase, such as Ag₃SbS₃ and Sb₂S₃ among AgSbS₂ particles and simplify the complicated steps in synthesizing AgSbS₂ via conventional methods, the cubic AgSbS₂ silk-like nanoflowers with well-defined crystalline structure were synthesized by the one-step, facile and practical solvothermal chemical process. The results show that the as-prepared stoichiometric AgSbS₂ nanoflowers with the diameter of 1 µm are comprised of silk-like ultrathin nanoflakes. Moreover, the possible formation mechanism of AgSbS₂ silk-like nanoflowers with PSS (poly (sodium-p-styrenesul-fonate)) is studied. Furthermore, the AgSbS₂ nanoflowers exhibit a broad absorption and high value of incident photon to current conversion efficiency (IPCE) in visible light range, indicating that it is a promising photovoltaic absorption material.