This work reports the first conjugated polymer with multidirectional orientations and highlights its importance to the performance of devices. Specifically, a novel conjugated polymer N2200-NDI combining poly(naphthalenediimide-alt-bithiophene) backbone with naphthalenediimide (NDI) side units has been synthesized and characterized. N2200-NDI possesses not only a wide absorption spectra and deep energy levels but also a distinctive aggregation state. As confirmed by two-dimensional grazing-incidence X-ray scattering, the polymer backbone prefers a typical face-on packing mode, while NDI side units present an oblique arrangement with a lateral rotation dihedral angle of 30 degrees. Such unique multidirectional orientations endow N2200-NDI with multichannel electron transport. Furthermore, the space-charge-limited current electron mobility, short-circuit current density, and fill factor of PBDB-T:N2200-NDI-based solar cells are obviously positively correlated with the lateral diffraction intensity of NDI side units. These findings provide a new strategy to construct conjugated polymers with distinct charge transport property.