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Silicon oxide nanowires synthesized during carbonization of polyimide thin film on a silicon substrate exhibited marked enhancement in photoluminescence (PL) at 420 nm by prolonging the growth period. Maximum intensity was recorded when the nanowire diameter coarsened from 70 to 165 nm by extending the growth period from 1 to 3 h. The enhancement was attributed to the increase in concentration of neutral oxygen vacancies on the surface of the nanowires. It was also demonstrated that the PL peak can be shifted to 600 nm while maintaining the enhanced intensity by postannealing the nanowires in a reducing atmosphere.