Flower-like silver vanadium oxide (SVO) micropatterns were realized by femtosecond laser in situ writing from its precursor. Self-assembled petals irradiated by a femtosecond laser were observed standing on the substrate along the scanned routine assisted by the formation of silver seeds and plasmonic-mediated effects. By controlling the concentration of ammonium monovanadate and the laser exposure time, a different thickness of petals was manipulated from ∼100 nm to micrometers. The SVO products were confirmed Ag4V2O7, AgVO3, and part of Ag3VO4 by x-ray diffraction (XRD) measurement. Photon-driven self-assembly for in situ fabrication of microstructures looks to be an effective and facile technique for SVO and other functional compounds.