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An efficient BiVO 4 nanocatalyst with Erbium (Er) and Yttrium (Y) doping was synthesized via a facile microwave irradiation route and the obtained materials were further characterized through various techniques such as p-XRD, FT-IR, FE-SEM, HR-TEM, UV–Vis DRS, PL, LSV, and EISanalysis. The obtained results revealed that the rare metals induce the stabilization of the monoclinic-tetragonal crystalline structure with a distinct morphology. The yttrium doped BiVO 4 (Y–BiVO 4) monoclinic-tetragonal exhibited anefficient photoelectrochemical water splitting and photocatalytic performanceare compared to bare BiVO 4. TheY-BiVO 4 indicated increased results of photocurrent of 0.43 mA/cm2and bare BiVO 4 0.24 mA/cm2. Also, the Y-doped BiVO 4 nanocatalyst showed the maximum photocatalytic activity for the degradation of MB, MO, and RhB. A maximum degradation of 93%, 85%, and 91% was achieved for MB, MO, and RhB respectively, within 180 min under the visible light illumination. The photocatalytic decomposition of acetaldehyde also was performed. The improved photoelectrochemical water splitting and photocatalytic activity are due to the narrowing the bandgap, leading to extending the photoabsorption capability and reducing the recombination rate of photoexcited electron-hole pairs through the formation inner energy state of the rare earth metals. The current study disclosed that the synthesis of nanomaterials with crystal modification could be a prospectivecontender forhydrogen energy production as well as to the photocatalytic degradation of organic pollutants.To the best of our knowledge, both photocatalytic and photoelectrochemical studies were never been reported before for this type of material. [Display omitted] • BiVO 4 nanocatalystdoped with Erbium (Er) and Yttrium (Y) was synthesized. • Nanocatalysts were characterized by p-XRD, FT-IR, FE-SEM, HR-TEM, UV–Vis DRS, PL, LSV, and EIS. • Raman analysis confirms the successful incorporation of rare metals into the BiVO 4 structure. • Y–BiVO 4 exhibited efficient photoelectrochemical water splitting and photocatalytic performance. • Maximum degradation of 93%, 85%, and 91% was achieved for MB, MO, and RhB respectively. [ABSTRACT FROM AUTHOR]