For the first time, nano-scale aluminum hypophosphite (AlPO2) was simply obtained in a two-step milling process and applied in preparation of epoxy nanocomposites varying concentration (0.1, 0.3, and 0.5 wt.% based on resin weight). Studying the cure kinetics and thermal stability of these nanocomposites would pave the way toward the design of high-performance nanocomposites for special applications. Scanning electron microscopy (SEM) and transmittance electron microscopy (TEM) revealed AlPO2 particles having domains less than 60 nm with high potential for agglomeration. Excellent (at heating rate of 5 °C/min) and Good (at heating rates of 10, 15 and 20 °C/min) cure states were detected for nanocomposites under nonisothermal differential scanning calorimetry (DSC). While the dimensionless curing temperature interval (ΔT*) was almost equal for epoxy/AlPO2 nanocomposites, dimensionless heat release (ΔH*) changed by densification of polymeric network. Quantitative cure analysis based on isoconversional Friedman and Kissinger methods gave rise to the kinetic parameters such as activation energy and the order of reaction as well as frequency factor. Variation of glass transition temperature (Tg) was monitored to explain the molecular interaction in the system, where Tg increased from 73.2 °C for neat epoxy to just 79.5 °C for the system containing 0.1 wt.% AlPO2. Moreover, thermogravimetric analysis (TGA) showed that nanocomposites were thermally stable.