Nanomaterials with intense near-infrared (NIR) absorption exhibit effective photon-to-thermal energy transfer capabilities and can generate heat to ablate cancer cells, thus playing a pivotal role in photothermal cancer therapeutics. Herein, hydrophilic flower-like bismuth sulfur (Bi₂S₃) superstructures with uniform size and improved NIR absorption were controllably synthesized via a facile solvothermal procedure assisted by polyvinylpyrrolidone (PVP), which could adjust the product morphology. Induced by an 808-nm laser, the as-prepared Bi₂S₃ nanoflowers exhibited much higher photothermal conversion efficiency (64.3%) than that of Bi₂S₃ nanobelts (36.5%) prepared in the absence of PVP. This can be attributed not only to the Bi₂S₃ nanoflower superstructures assembled by 3-dimensional crumpled-paper-like nanosheets serving as many laser-cavity mirrors with improved reflectivity and absorption of NIR light but also to the amorphous structures with a lower band gap. Thus, to achieve the same temperature increase, the concentration or laser power density could be greatly reduced when using Bi₂S₃ nanoflowers compared to when using Bi₂S₃ nanobelts, which makes them more favorable for use in therapy due to decreased toxicity. Furthermore, these Bi₂S₃ nanoflowers effectively achieved photothermal ablation of cancer cells in vitro and in vivo. These results not only supported the Bi₂S₃ nanoflowers as a promising photothermal agent for cancer therapy but also paved an approach to exploit new agents with improved photothermal efficiency.