A novel organic–inorganic eutectic phase change material (PCM) based on sodium acetate trihydrate (SAT) and polyethylene glycol (PEG) was developed to meet the needs of heat recovery and building heating. Three kinds of PEG with different molecular weights were selected to form organic–inorganic eutectic PCM with SAT. The thermal properties of three series of SAT-PEG eutectic PCM were compared based on DSC results, focusing on the impact of PEG addition on the phase change temperature and enthalpy of SAT, as well as the melting uniformity. The inhibitory effects of two nucleating agents on the supercooling of SAT-PEG eutectic PCM were systematically investigated. The effect of PEG on the crystallization behavior of SAT was studied using a metallographic microscope. To evaluate the thermal reliability of the SAT-PEG eutectic PCM, 600 cycles of melting–solidification experiments were conducted. Experimental results show that SAT can form eutectic PCMs with PEG200, PEG600, and PEG6000, respectively, with high enthalpy and excellent melting uniformity. The phase change temperature ranged from 55 °C to 60 °C and the enthalpy was as high as 250–280 kJ/kg. The results of the cooling curves show that 10 wt% tetrasodium pyrophosphate decahydrate (TPD) can reduce the supercooling degree to less than 1 °C. Significantly, all three series of SAT-PEG eutectic PCMs exhibit exceptional thermal reliability after 600 cycles of melting–solidification, with shifts in the phase change temperatures and enthalpies of less than 4%. XRD diffraction patterns showed that SAT, PEG, and TPD were physically mixed without a chemical reaction to form new substances. Microscopic images reveal that the addition of PEG preserves the original needle-shaped crystal morphology of SAT while reducing its crystal size. The rapid formation of small crystals can provide more nucleation points and expedite crystallization, thereby enhancing the heat release capabilities of the PCM.