Temperature measurement at the nanoscale is of paramount importance in the fields of nanoscience and nanotechnology, and calls for the development of versatile, high-resolution thermometry techniques. Here, the working principle and quantitative performance of a cost-effective nanothermometer are experimentally demonstrated, using a molecular spin-crossover thin film as a surface temperature sensor, probed optically. We evidence highly reliable thermometric performance (diffraction-limited sub-µm spatial, µs temporal and 1 °C thermal resolution), which stems to a large extent from the unprecedented quality of the vacuum-deposited thin films of the molecular complex [Fe(HB(1,2,4-triazol-1-yl)3)2] used in this work, in terms of fabrication and switching endurance (>107 thermal cycles in ambient air). As such, our results not only afford for a fully-fledged nanothermometry method, but set also a forthcoming stage in spin-crossover research, which has awaited, since the visionary ideas of Olivier Kahn in the 90’s, a real-world, technological application.