The development of new x-ray and γ-ray spectrometers based on AlInP photodiodes with increased quantum detection efficiency and improved energy resolution is reported. The spectroscopic responses of two AlInP p+–i–n+ mesa photodiodes (10 μm i layer, the thickest so far reported) were investigated at photon energies from 4.95 to 88.03 keV; the detectors and preamplifier were operated at 30 °C. Energy resolutions (full width at half maximum) of 750 ± 40 eV and 850 ± 30 eV at 4.95 keV were achieved with the two detectors. The energy resolution deteriorated with increasing photon energy; this was in accordance with the increasing Fano noise with energy and suggested negligible incomplete charge collection noise across the photon energy range investigated. The measured voltage output of each spectrometer was found to be linear as a function of incident x-ray photon energy. The count rate (measured at 8.63 keV) was also found to linearly increase with incoming x-ray photon flux for the investigated spectrometers. These results, which were obtained using the thickest AlInP photodiodes produced so far, suggest that AlInP detectors are highly promising candidates for future uncooled x-ray and γ-ray spectrometers.