This report describes the synthesis of 4-organoselenylisoxazoles via FeCl(3)/RSeSeR-mediated intramolecular cyclization of alkynone O-methyloximes. The optimized conditions allowed the cyclization to proceed at room temperature under ambient atmosphere, and the reaction requires a short time to be completed. The reaction conditions tolerated neutral, electron-donating and electron-withdrawing groups present in both substrates, alkynone O-methyloximes and diorganyl diselenides. Treatment of 4-organoselenylisoxazoles with n-butyllithium, followed by trapping with electrophiles, furnished the functionalized isoxazoles in good yields. The obtained products also proved to be suitable substrates for the preparation of 4-bromoisoxazoles via Br/Se exchange reaction.