This investigation details the formation of polymer network trilayer laminates formed by thiol-X click chemistries, and their subsequent implementation and evaluation for quadruple shape memory behavior. Thiol-Michael addition and thiol-isocyanate-based crosslinking reactions were employed to fabricate each of the laminate's layers with independent control of the chemistry and properties of each layer and outstanding interlayer adhesion and stability. The characteristic features of step-growth thiol-X reactions, such as excellent network uniformity and narrow thermal transitions as well as their stoichiometric nature, enabled fabrication of trilayer laminates with three distinctly different glass transition temperatures grouped within a narrow range of 100 °C. Through variations in the layer thicknesses, a step-wise modulus drop as a function of temperature was achieved. This behavior allowed multi-step programming and the demonstration and quantification of quadruple shape memory performance. As is critical for this performance, the interface connecting the layers was evaluated in stoichiometric as well as off-stoichiometric systems. It was shown that the laminated structures exhibit strong interfacial binding and hardly suffer any delamination during cyclic material testing and deformation.