Multifunctional recyclable glassy polymeric materials (GPMs) are sustainable substitutes for high-performance protective materials in aerospace, transportation, construction, and electronics; however, only a few such materials have been reported. This study presents a novel material design including the modular construction, utilization of self-reinforcing polysilsesquioxane (POSS), and self-enrichment strategy to integrate multifunctions in recyclable GPMs. Specifically, rigid self-reinforcing thiol-capped POSS (module 1) are connected with isocyanate-terminated polyurethane precursors (module 2) by forming dynamic thiourethane covalent bonds to fabricate recyclable GPMs. Particularly, based on the modular construction and self-enrichment strategy, functional module 3 can be introduced to endow recyclable GPMs with programmable multifunctionality. Demonstrating remarkable properties, including high transparency (>85% transmittance), hardness (up to 5H), good flexibility, and exceptional wear resistance, these materials also exhibit impressive shape reconfigurability and robustness after numerous thermal recycling or remolding cycles. Moreover, the introduction of functional module 3 (e.g., polydimethylsiloxane prepolymer) can self-enrich onto the surface to endow the materials with anti-liquid adhesion, self-cleaning, and deicing properties while having a slight impact on their mechanical properties. This study presents a universal and tunable approach for the future design of multifunctional recyclable GPMs applicable in flexible electronics, aircraft vehicles, and architectural windows.