In this paper, BiVO₄ nanostructures with different morphologies were synthesized via hydrothermal method with the assistances of polyvinyl pyrrolidone (PVP), cetyltrimethyl ammonium bromide (CTAB), and sodium dodecyl benzene sulfonate (SDBS). The structures and the photocatalytic activities of BiVO₄, PVP-assisted BiVO₄ (BiVO₄-PVP), CTAB-assisted BiVO₄ (BiVO₄-CTAB), and SDBS-assisted BiVO₄ (BiVO₄-SDBS) were characterized systematically by various techniques and organic pollution degradation experiment. The photocatalytic performance of these nanoparticles on the degradation of rhodamine B (RhB) was as follows: BiVO₄-SDBS > BiVO₄-CTAB > commercial photocatalyst P25 (under UV light irradiation) > BiVO₄ > BiVO₄-PVP > commercial photocatalyst P25 (under visible light irradiation). Irregular flake-stacked BiVO₄-SDBS exhibited smaller crystallite size and larger specific surface area (3.9 m²/g) than irregular blocky BiVO₄, rice-grained BiVO₄-PVP, and polyhedral BiVO₄-CTAB, leading to the shortened diffusion distance of electron-hole pairs and the enhanced separation efficiency of photogenerated electron-hole pairs. Due to the efficient electron-hole pairs separation and the enhanced visible light absorption, 2.0 g/L of BiVO₄-SDBS showed the complete photocatalytic degradation rate of 100% on RhB (10 mg/L, 50 mL) in aqueous solution with pH 2 after irradiating under visible light for 40 min. The holes and superoxygen radical played vital roles in the photocatalytic degradation of RhB. Such investigation provides guidance for the rational design of visible light-active photocatalysts for the degradation of organic pollutants in wastewater.