Fully conjugated ladder copolymers have attracted considerable attention due to their unique fused-ring structure and optoelectronic properties. In this study, two fully conjugated ladder naphthalene diimide (NDI) copolymers, P(NDI-CZL) and P(NDI-TTL) with imine-bridged structures are presented in high yields. Both of the two copolymers have good solubility and high thermal stability. The corresponding compounds with the same structure as the copolymers were synthesized as model system. The yields for each step of the synthesis of the model compounds are higher than 95%. These results suggest that P(NDI-CZL) and P(NDI-TTL) can be synthesized successfully with fewer structural defects. The structures and optoelectronic properties of compounds and copolymers are investigated by NMR, fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV-vis), and cyclic voltammetry (CV). Both in solution and as a thin film, the two copolymers show two UV-vis absorption bands (around 300–400 nm and 400–750 nm) and a very weak fluorescence. The collective results suggest that the two fully conjugated ladder copolymers can be used as potential acceptor materials.