Our research group has recently found excellent shape-memory response in “thiol-epoxy” thermosets obtained with click-chemistry. In this study, we use their well-designed, homogeneous and tailorable network structures to investigate parameters for better control of the shape-recovery process. We present a new methodology to analyse the shape-recovery process, enabling easy and efficient comparison of shape-memory experiments on the programming conditions. Shape-memory experiments at different programming conditions have been carried out to that end. Additionally, the programming process has been extensively analysed in uniaxial tensile experiments at different shape-memory testing temperatures. The results showed that the shape-memory response for a specific operational design can be optimized by choosing the correct programming conditions and accurately designing the network structure. When programming at a high temperature (T » Tg), under high network mobility conditions, high shape-recovery ratios and homogeneous shape-recovery processes are obtained for the network structure and the programmed strain level (eD). However, considerably lower stress and strain levels can be achieved. Meanwhile, when programming at temperatures lower than Tg, considerably higher stress and strain levels are attained but under low network mobility conditions. The shape-recovery process heavily depends on both the network structure and eD. Network relaxation occurs during the loading stage, resulting in a noticeable decrease in the shape-recovery rate as eD increases. Moreover, at a certain level of strain, permanent and non-recoverable deformations may occur, impeding the completion and modifying the whole path of the shape-recovery process.