By combining density functional theory with the non-equilibrium Green’s function method, we conducted a first-principles investigation of spin-dependent transport properties in a molecular device featuring a dynamic covalent chemical bridge connected to zigzag graphene nanoribbon electrodes. The effects of spin-filtering and spin-rectifying on the I–V characteristics are revealed and explained for the proposed molecular device. Interestingly, our results demonstrate that all three devices exhibit significant single-spin-filtering behavior in parallel (P) magnetization and dual-spin-filtering effects in antiparallel (AP) configurations, achieving nearly 100% spin-filtering efficiency. At the same time, from the I–V curves, we find that there is a weak negative differential resistance effect. Moreover, a high rectifying ratio is found for spin-up electron transport in AP magnetization, which is explained by the transmission spectrum and local density of state. The fundamental mechanisms governing these phenomena have been elucidated through a systematic analysis of spin-resolved transmission spectra and spin-polarized electron transport pathways. These results extend the design principles of spin-controlled molecular electronics beyond graphene-based systems, offering a universal strategy for manipulating spin-polarized currents through dynamic covalent interfaces. The nearly ideal spin-filtering efficiency and tunable rectification suggest potential applications in energy-efficient spintronic logic gates and non-volatile memory devices, while the methodology provides a framework for optimizing spin-dependent transport in hybrid organic–inorganic nanoarchitectures. Our findings suggest that such systems are promising candidates for future spintronic applications.