Methoxycarbonylsulfenyl chloride is a sulfenyl carbonyl compound. Photoinduced fragmentations of methoxycarbonylsulfenyl chloride is investigated in the gaseous phase by using synchrotron radiation and multicoincidence techniques. The molecular structure and conformational properties of methoxycarbonylsulfenyl chloride is studied in the gas and solid phases by gas electron diffraction, low-temperature X-ray diffraction and vibrational spectroscopy. The anomeric and mesomeric effects in methoxycarbonylsulfenyl chloride is reported.