Van der Waals integration with abundant two-dimensional materials provides a broad basis for assembling functional devices. In a specific van der Waals heterojunction, the band alignment engineering is crucial and feasible to realize high performance and multifunctionality. Here, we design a ferroelectric-tuned van der Waals heterojunction device structure by integrating a GeSe/MoS2 VHJ and poly (vinylidene fluoride-trifluoroethylene)-based ferroelectric polymer. An ultrahigh electric field derived from the ferroelectric polarization can effectively modulate the band alignment of the GeSe/MoS2 heterojunction. Band alignment transition of the heterojunction from type II to type I is demonstrated. The combination of anisotropic GeSe with MoS2 realizes a high-performance polarization-sensitive photodetector exhibiting low dark current of approximately 1.5 pA, quick response of 14 μs, and high detectivity of 4.7 × 1012 Jones. Dichroism ratios are also enhanced by ferroelectric polarization in a broad spectrum from visible to near-infrared. The ferroelectric-tuned GeSe/MoS2 van der Waals heterojunction has great potential for multifunctional detection applications in sophisticated light information sensing. More profoundly, the ferroelectric-tuned van der Waals heterojunction structure provides a valid band-engineering approach to creating versatile devices.