<p>Control crosslink network and chain connectivity are essential to develop shape memory polymers (SMPs) with high shape memory capabilities, adjustable response temperature, and satisfying mechanistical properties. In this study, novel poly(<i>ε</i>-caprolactone) (PCL)-poly(2-vinyl)ethylene glycol (PVEG) copolymers bearing multi-pendant vinyl groups is synthesized by branched-selective allylic etherification polymerization of vinylethylene carbonate (VEC) with linear and tetra-arm PCLs under a synergistic catalysis of palladium complex and boron reagent. Facile thiol-ene photo-click reaction of PCL-PVEG copolymers with multifunctional thiols can rapidly access a serious crosslinked SMPs with high shape memory performance. The thermal properties, mechanical properties and response temperature of the obtained SMPs are tunable by the variation of PCL prepolymers, vinyl contents and functionality of thiols. Moreover, high elastic modulus in the rubbery plateau region can be maintained effectively owing to high-density topological networks of the PCL materials. In addition, the utility of the present SMPs is further demonstrated by the post-functionalization <i>via</i> thiol-ene photo-click chemistry.</p>