Polystyrene (PS) microspheres were synthesized by emulsifier-free emulsion polymerization and arranged in an array of closely packed, opal-like photonic crystals by slow self-assembly through dip coating. This periodic array of PS microspheres was then employed as a rapid qualitative sensor for methanol and ethanol. Both solvents could be detected rapidly based on the routes of their reflection coordinates in the chromaticity diagram or directly by the naked eye on the basis of the change in color within 1 min once a solvent sample had been placed on the PS photochromic sensor. This opal-like PS sensor can thus not only be employed as a rapid sensor for methanol and ethanol but can also be used as a powerful tool for the fast screening of illicit drugs and toxic chemicals during forensic investigations. (C) 2016 Elsevier B.V. All rights reserved.