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We found that the grain size of V2O5 thin films produced by pulsed laser ablation strongly influences their optical characteristics. The decrease in the optical band gap associated with a change in spectral transmittance of the pulsed laser deposited V2O5 films are mainly due to structure evolution from amorphous to crystalline state and size evolution and distribution characteristics of the grains as a function of increasing growth temperature. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)