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In this work, a porous silicon nanostructure has been fabricated by electrochemical means and used as a thermal sensor. The thermo-optic effect in the near infrared region has been experimentally studied based on spectroscopy measurements. Values of the thermo-optic coefficient between 3.2 and 7.9·10−5 K−1 have been obtained, depending on the porosity, reaching a maximum thermal sensitivity of 91 ± 3 pm/°C during the experiments carried out with the fabricated samples. Additionally, the oxidation process of the sensor at temperatures below 500 K has been studied, showing that the growth of the silicon oxide was dependent on the characteristics of the porous layers. Based on the experimental results, a mathematical model was developed to estimate the evolution of the oxidation process as a function of porosity and thickness. © The Author(s) 2019. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. [DOI: 10.1149/2.0341906jes]