A novel, reliable, and sensitive approach for the determination of chlorine by sector field inductively coupled plasma mass spectrometry (SF-ICPMS) using photochemical vapor generation for sample introduction is presented. Methyl chloride is generated from different chlorine species in a flow-through photochemical reactor using a 1% solution of acetic acid containing 7.5 μg g–1 of Cu2+. The volatile product is directed by an argon carrier gas to a gas–liquid separator and introduced into the instrument. A sample flow rate at 1.7 mL min–1 and a 45 s irradiation time provided a 74-fold enhancement in sensitivity compared to conventional nebulization. A blank-limited detection limit of 0.5 ng g–1 for chloride, suitable for quantitation at trace levels, was achieved. The proposed method was validated by analysis of two certified reference materials, NIST SRM 1568b rice flour and SRM 1571 orchard leaves, with satisfactory results, as well as three varieties of bottled water, achieving spike recoveries between 101% and 105%.