Anisotropic charge transport plays a pivotal role in clarifying the conductivity mechanism in direct X‐ray detection to improve the detection sensitivity. However, the anisotropic photoelectric effect of semiconductive single crystal responsive to X‐ray is still lacking of theoretical and experimental proof. The semiconductive coordination polymers (CPs) with designable structures, adjustable functions, and high crystallinity provide a suitable platform for exploring the anisotropic conductive mechanism. Here,the study first reveals a 1D conductive transmission path for direct X‐ray detection from the perspective of structural chemistry. The semiconductive copper(II)‐based CP 1 single crystal detector exhibits unique anisotropic X‐ray detection performance. Along the 1D π–π stacking direction, the single crystal device (1‐SC‐a) shows a superior sensitivity of 2697.15 µCGyair−1 cm−2 and a low detection limit of 1.02 µGyair s−1 among CPs‐based X‐ray detectors. This study provides beneficial guidance and deep insight for designing high‐performance CP‐based X‐ray detectors.