Monoclinic bismuth vanadate (m-BiVO₄) with novel hollow peanut-like morphology was synthesized for the first time using L-lysine as surfactant. The use of L-lysine and the crystallization procedure is indispensable in getting the peanut-like morphology. The photocatalytic activity of the m-BiVO₄ samples under solar-light irradiation was evaluated for degradation of crystal violet and methylene blue. Crystallization and calcination temperature are important factors affecting the photocatalytic activity of m-BiVO₄, and best performance was observed over the sample that crystallized at 160 °C in the presence of L-lysine and subsequently subjected to calcination at 550 °C. The as-prepared BiVO₄ showed good stability in catalyst recycling. Based on the results of XRD, XPS, FESEM, TEM (HRTEM), UV-vis diffuse reflectance spectroscopy, and N₂ adsorption–desorption characterization, the good photocatalytic activity of the m-BiVO₄ sample is attributed to its unique hollow peanut-like morphology and pure monoclinic phase of high crystallinity.