A facile and bio-inspired route for the preparation of pure and highly crystalline metastable α-AgVO 3 is presented. Three kinds of proteins (bovine hemoglobin, bovine serum albumin, and lysozyme) were employed as inducer, which had substantial effects on the nucleation and growth of α-AgVO 3 . Moreover, the amount of proteins also played a key role over the morphology and crystalline of products. The VO3-/protein complex acted as a driver to induce the formation of metastable phase, which was confirmed by resonance Rayleigh scattering and UV–vis absorption spectra. The results indicated that tailoring an interaction between protein and inorganic molecules was the key in bio-inspired selective synthesis of metastable phase, which may find applications in the design of other new functional inorganic materials.