A prototype 200 μm diameter Al0.52In0.48P p+-i-n+ mesa photodiode (2 μm i-layer) was characterised at temperatures from 100 °C to −20 °C for the development of a temperature tolerant photon counting X-ray spectrometer. At each temperature, X-ray spectra were accumulated with the AlInP detector reverse biased at 0 V, 5 V, 10 V, and 15 V and using different shaping times. The detector was illuminated by an 55Fe radioisotope X-ray source. The best energy resolution, as quantified by the full width at half maximum (FWHM) at 5.9 keV, was observed at 15 V for all the temperatures studied; at 100 °C, a FWHM of 1.57 keV was achieved, and this value improved to 770 eV FWHM at −20 °C. System noise analysis was also carried out, and the different noise contributions were computed as functions of temperature. The results are the first demonstration of AlInP's suitability for photon counting X-ray spectroscopy at temperatures other than ≈20 °C.