We reported a simple and economical SDS (sodium dodecyl sulfate) assisted BiVO₄ solvothermal synthesis of BiVO₄ nanostructures. The implementation of pristine and SDS assisted BiVO₄ nanostructure as photoanode in photoelectrochemical (PEC) water splitting was investigated. The good crystalline nature, defects present in the material, recombination nature and vibrational properties of the synthesized BiVO₄ nanostructures have been analyzed and confirmed by XRD, Raman, PL and FTIR studies. The constructed nanoflower oriented morphology combined with nanorods for SDS assisted BiVO₄ have been examined by SEM studies. The optical band gap differences were observed as 2.35 and 2.31 eV for pristine and SDS assisted BiVO₄ nanostructures respectively. The higher photocurrent density of 5.8 μA/cm² at 0.5 V versus RHE with lower flat band potential of -0.75 V revealed for SDS assisted BiVO₄ nanostructured photoanodes. Good conductivity, higher charge separation efficiency and 52% photocurrent retention under illumination was reported over 7200 s for the same efficient photoanode. These results suggested the substantial possibility of BiVO₄ nanostructures synthesized by using SDS surfactant could be utilized as efficient photoanodes for PEC water splitting applications.