I(+1) formed by reacting iodine with KIO3 in 96% sulfuric acid is partly in the form of I2O that can be extracted in dichloromethane (DCM). The extraction process is an interesting coupling between phase transfer and chemical reactions allowing to obtain solutions containing nearly no iodine. I2O solutions can also be obtained in other chlorinated solvents and forms probably an ionic complex in acetonitrile. UV-vis spectra are presented (epsilon (I2O, 442 nm) = 259 in DCM). Distillations of I2O solutions and gas phase diffusion at laboratory temperature show that I2O is a volatile compound that should be considered in atmospheric chemistry.