A novel sensor for gaseous iodine has been developed using a combination of sol-gel processing and planar integrated optical waveguiding technologies. The sensing principle is based on the detection of a charge transfer complex formed between iodine and phenyl groups that have been incorporated into a porous, methylated glass film. The glass film was prepared from siloxane precursors by the sol-gel method. Sensors were fabricated by coating the film over a single-mode planar waveguide. Light was coupled into and out of the laminate structure using integral grating couplers, and formation of the charge transfer complex was monitored as attenuated total reflection of the guided wave. The sensor exhibits a linear response to I(2) in the range of 100 ppb to 15 ppm with response and recovery times less than 15 s. The response is selective to 4 ppm iodine in the presence of 10 ppm chlorine and is stable for at least 3 months.