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Evanescent field optical sensors are accurately designed for hydrocarbon monitoring in water. Various kinds of waveguide sensors are optimized by considering a polydimethylsiloxane polymeric overlay as sensor region. The simulation results suggest that the selection of a suitable waveguide cross section can enhance the sensor performance. In particular, the hollow waveguide sensor exhibits very intriguing performance, the absorbance being quite linear with respect to the contaminant concentration. For the toluene pollution the absorbance exhibits a slope S A TE = 2.52 × 10 −2 ppm −1 for a waveguide reference length L = 1.18 mm. In order to simultaneously detect different pollutants in water such as toluene, benzene, chlorobenzene and ethilbenzene, an array of four miniaturized hollow waveguide sensors is designed.