Novel block copolymers were synthesized for the first time via nitroxide-mediated polymerization (NMP) using ethylene glycol dicylopentenyl methacrylate (EGDEMA), which has a pendent double bond in the norbornene group, and farnesene (Far), a terpene-based diene. Homopoly(EGDEMA)) was synthesized successfully using Dispolreg 007 initiator without any co-monomer as typically required of NMP, and the macroinitiator was chain-extended with Far making poly(EGDEMA-b-Far) diblock copolymers. Due to the relatively low glass transition temperature (Tg) of poly(EGDEMA), the methacrylate block was also copolymerized statistically with isobornyl methacrylate (iBOMA) to add stiffness, then chain-extended with Far. Additionally, the pendent double bond of EGDEMA allowed for thiol-ene clicking of POSS units for further functionalization of these block copolymers. However, the conjugation efficiency of the thermally initiated thiol-ene clicking was low and resulted in low POSS incorporation (1.6–10 mol%), especially for block copolymers that included iBOMA due to its increased stiffness and steric hindrance. Nonetheless, the added POSS improved the thermal stability by minimizing the degradation of the 1,4-addition Far units, as well as the degradation of isobornyl units of iBOMA. The mechanical strength was also increased as POSS units reinforced the physical crosslinks of these block copolymers as shown by an increase in linear viscoelastic regions. Distinct Tgs were observed for the respective elastomeric poly(Far) block (~-70 °C) and thermoplastic block (30 °C for poly(EGDEMA) and 110 °C for poly(EGDEMA-co-iBOMA)), therefore suggesting microphase separation. An increase in Tg was also observed in all polymers with added POSS, further confirming the added stiffness provided by POSS. These poly(EGDEMA-b-Far) and poly(EGDEMA-co-iBOMA-b-Far) show great versatility as alternative TPE materials, with improved mechanical and thermal properties added by functionalization of POSS.