The XLD eff was calculated during the reaction and plotted against the elastic modulus in Similar to elastic modulus, the Tg shows an increasing trend by conversion which is in agreement with the results obtained from DSC at different conversions. The lowest calculated Tg was observed for S-6OH system, attributed to the late formation of the network and higher chains mobility. In contrast, in the L-6OH system, a rigid cross-linked network resulted in a higher calculated Tg. XLD eff shows a strong correlation with calculated Tg (p=0.95), providing a good prediction of thermal properties. Therefore, in contrast to conversion and XLD, XLD eff gives a more comprehensive representation for microstructural features that affect the thermo-mechanical performance of the network. Our multi-scale modeling scheme allowed us to capture the most significant features of complex network topologies which is not a trivial task through conventional modeling and experimental approaches. As a result, our simulations provided a deeper understanding of structure-property relationships for complex polymer networks, which led to the introduction of XLD eff , a single parameter for the assessment of thermo-mechanical properties. Therefore, it can be tremendously useful in streamlining the in-silico design and optimization of the microstructure of complex polymer networks. Furthermore, our simulations provide a clear picture of the curing process of these networks, which potentially informs the formulation optimization. For instance, there is common knowledge that high-solid acrylic resins need to reach very high conversions to give acceptable thermo-mechanical properties and our results unravel the reasons behind this. High-solid resins (similar to our short chain, S-6OH) form fewer loops compared to longer acrylic resins (e.g., L-6OH), and therefore, a higher proportion of cross-linkers create connections that are elastically more effective by bonding to more distinct polymer chains.