The demand for the development of more promising n-type semiconducting polymers with excellent electron mobilities and air stabilities is growing fast. In this study, we designed and synthesized a series of new dual imide-functionalized derivative-based regioregular D-A(1)-D-A(2) copolymers with different side chains (namely, PNT-R, R = 2-decyltetradecyl (DT), 2-octadecyldodecyl (OD), and 2-hexyldecyl (HD)). These new polymers PNT-R showed strong electron affinities with deep lowest unoccupied molecular orbital (LUMO) levels down to -4.01 eV, indicating that they are promising electron-transporting materials. To optimize the electron mobility, side-chain engineering was adopted. Thus, the effects of the side-chain length on their optoelectronic and charge-transport properties as well as the performances of all-polymer solar cells (all-PSCs) were systematically investigated. Shortening the side-chain length significantly expanded the absorption range, deepened the LUMO energy level, strengthened the molecular packing properties, and developed more crystalline microstructures in the solid state, as evidenced by the ultraviolet-visible absorption spectra, cyclic voltammetry, synchrotron two-dimensional grazing-incidence wide-angle X-ray scattering, and atomic force microscopy measurements. Consequently, the highest electron mobility of 1.05 cm(2) V-1 s(-1) was achieved in PNT-HD-based organic thin-film transistors (OTFTs). Also, PNT-R polymers were successfully applied as electron acceptors in all-PSCs. In good agreement with the OTFT results, the highest power conversion efficiency of 6.62% was obtained for the PNT-HD-blend film due to its excellent short-circuit current (J(sc)) value (12.07 mA cm(-2)), which was much higher than that of the PNT-DT- and PNT-OD-based all-PSCs (7.67 and 10.19 mA cm(-2), respectively). By further investigating the dependence of the J(sc) and open-circuit voltage (V-oc) on the illuminated light intensity (P), the high J(sc) value of the PNT-HD-based device was found to originate from its highly suppressed mono- and bimolecular recombination as well as efficient exciton dissociation and charge transfer at the donor-acceptor interfaces. Overall, this study provides insights into the naphthalenediimide-based regioregular D-A(1)-D-A(2) copolymers used in all-PSCs and offers important design guidelines for future development of n-type semiconducting polymers.