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The selective detection of pollutants in water in a laboratory scenario has been presented by authors exploiting low-cost optical biosensors based on plastic optical fibers (POFs) and biological or biomimetic receptors. So, for instance, the detection in water of naphthalene, perfluoroalkyl substances (PFAs) and polyfluoroalkyl substances have been investigated with interesting detection limits when compared to those obtained by using different expensive traditional approaches (e.g., liquid chromatography-mass spectrometry with high performances). In this article, we have developed and tested a novel approach used in a smart measuring system to use POF sensors in situ for the remote measures of pollutants in water for smart cities applications. More specifically, we have used different water–glycerin solutions to test the novel sensor system based on a Raspberry Pi connected to the Internet and to a spectrometer, a light source, a POF sensor, and two computers connected to Internet used as client and server. [ABSTRACT FROM AUTHOR]