In this paper, a novel nanocrystalline composite material of hydroxyapatite (HA)/polyvinyltrimethoxysilane (PVTMS)/iron(II)chloride tetrahydrate (Cl2FeH8-O4) with hexagonal structure is proposed for the fabrication of a gas/temperature sensor. Taking into account the sensitivity of HA to high temperatures, to prevent the collapse and breakdown of bonds and the leakage of volatiles without damaging the composite structure, a freeze-drying machine is designed and fabricated. X-ray diffraction, FTIR, SEM, EDAX, TEM, absorption and photoluminescence analyses of composite are studied. XRD is used to confirm the material structure and the crystallite size of the composite is calculated by the Monshi–Scherrer method, and a value of 81.60 ± 0.06 nm is obtained. The influence of the oxygen environment on the absorption and photoluminescence measurements of the composite and the influence of vaporized ethanol, N2 and CO on the SiO2/composite/Ag sensor device are investigated. The sensor with a 30 nm-thick layer of composite shows the highest response to vaporized ethanol, N2 and ambient CO. Overall, the composite and sensor exhibit a good selectivity to oxygen, vaporized ethanol, N2 and CO environments.