A tandem synthesis for structurally novel 3-chloro-4-iodoisoxazoles was developed by simply mixing 1-copper (I) alkynes, dichloroformaldoxime, and molecular iodine together. The combination of 1-copper (I) alkyne and molecular iodine was well used as a synthetic equivalent of 1-iodoalkyne without the need for tedious preparation, purification, and storage of 1-iodoalkyne.