All-polymer solar cells (all-PSCs) are proven to possess outstanding thermal and mechanical stabilities. However, concurrently achieving appropriate phase-separated pattern, efficient charge transportation, and adequate charge transfer between donor and acceptor components is still a challenge, and thus, only a few polymer-polymer bulk heterojunction (BHJ) blends have yielded BHJ device power conversion efficiency (PCE) values of >8%. Generally, polymer backbone substitutions may have a direct influence on the device performance. Thus, this report examines a set of wide bandgap polymer donor analogues composed of thienothiophene (TT) or thiazolothiazole (TTz) motif, and their all-PSC device performance with N2200. Results show that all-PSCs based on the imine-substituted derivative PBDT-TTz exhibit PCE values as high as 8.4%, which largely outperform the analogue PBDT-TT-based ones with PCEs of only 0.7%. This work reveals that the imine substitution in polymer backbones of PBDT-TTz not only increases the ionization potential (IP) and electron affinity (EA), narrows the optical gap (Eopt), but also has significantly impacts on the BHJ film morphologies. PBDT-TTz:N2200 BHJ blends present better miscibility, suppressed phase separation, much stronger crystallinity, and face-on ordering, which contribute to efficient exciton dissociation, charge transportation, and therefore, high-efficiency in all-PSCs. This study demonstrates that the imine-substituted polymers composed of TTz motif, which can be easily synthesized through a facile two-step procedure, are a promising class of wide-bandgap polymer donors for efficient all-PSCs.