Two-dimensional (2D) hybrid perovskites with intrinsic attributes of structural and optical anisotropy are holding a bright promise for polarization-sensitive photodetection. However, studies on self-powered detection to quite weak polarized light remain scarce in this 2D family. By incorporating an aromatic spacer into the 3D cubic prototype, we have successfully assembled a new 2D hybrid perovskite with a polar motif, (FPEA)2(MA)Pb2I7 (FMPI, where FPEA is 4-fluorophenethylammonium and MA is methylammonium). Its unique 2D quantum-well structure allows optical absorption dichroism with a large ratio of ∼3.15, and the natural polarity results in a notable bulk photovoltaic effect. Further, centimeter-size crystals (10 × 10 × 3 mm3) of FMPI were facilely obtained by the temperature cooling method, and its crystal-based detectors enable excellent self-powered detection of quite weak polarized light, showing a notable polarization-sensitive ratio (∼1.5), extremely low detection limit (∼100 nW/cm2), and antifatigued stability. The alloyed aromatic cationic spacers facilitate the polarity and enhanced phase stability. This study paves a way for further exploration of new 2D perovskite candidates toward optoelectronic device applications.