The effective control of film morphology and molecular packing in the out-of-plane direction of semiconductor polymers plays a critical role in governing charge carrier transport in the direction perpendicular to the substrate. In this study, a highly out-of-plane alignment of the n-type polymer P(NDI2OD-T2) film has been successfully achieved by horizontal rotation in a high magnetic field (HR-HMF). The out-of-plane alignment of the P(NDI2OD-T2) film has showed a change from 72% face-on to 98.2% face-on lamellar texture as well as a 1.6-fold increase of the π-π stacking crystalline correlation length compared with that of as-cast polymer films without HR-HMF-induced alignment. Meanwhile, the film with near-perfect face-on molecular packing exhibited more than 18-fold enhancement of electron mobility compared to the unaligned film. The excellent electrical performance achieved with the HR-HMF process indicates its application potential for fabricating high-performance sandwich-type organic electronic devices, such as solar cells and light-emitting diodes.