A facile and bio-inspired route for the preparation of pure and highly crystalline metastable alpha-AgVO3 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 alpha-AgVO3. 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. (C) 2011 Elsevier Inc. All rights reserved.