For the first time, the kinetics of isothermal curing and thermal degradation of polyethylene glycol maleate (pEGM)–based systems and their composites with mineral fillers were investigated in the presence of a benzoyl peroxide/N,N-Dimethylaniline redox-initiating system. DSC analysis revealed that the curing process at 20 °C can be described by the modified Kamal autocatalytic model; the critical degree of conversion (α_c) decreases with increasing content of the unsaturated polyester pEGM and in the presence of fillers. In particular, for unfilled systems, α_c was 0.77 for pEGM45 and 0.60 for pEGM60. TGA results demonstrated that higher pEGM content and the incorporation of fillers lead to increased thermal stability and residual mass, along with a reduction in the maximum decomposition rate (dTGₘₐₓ). Calculations using the Kissinger–Akahira–Sunose and Friedman methods also confirmed an increase in the activation energy of thermal degradation (E_a): E_KAS was 419 kJ/mol for pEGM45 and 470 kJ/mol for pEGM60, with the highest values observed for pEGM60 systems with fillers (496 kJ/mol for SiO₂ and 514 kJ/mol for CaCO₃). Rheological studies employing three-interval thixotropy tests revealed the onset of thixotropic behavior upon filler addition and an increase in structure recovery after deformation of up to 56%. These findings underscore the potential of pEGM-based systems for low-temperature curing and for the design of composite materials with improved thermal resistance.