In comparison to inorganic counterparts, organic semiconducting (OSC) crystalline films are promising for building large-area and flexible ionizing radiation detectors for X-ray imaging or dosimetry due to their tissue equivalence, simple processing and large-scale production accessibility. Fabrication processes, however, hinder the ability to generate aligned and large-area films with high carrier mobility. In this work, the space-confined melt process is used to produce highly orientated 4HCB (4-hydroxycyanobenzene) OSC films with a large area of 15 × 18 mm2. The out-of-plane direction of the 4HCB film is <001>, and the benzene rings are found to be extensively overlapped inside the in-plane direction, according to the XRD patterns. The film exhibits a high resistivity up to 1012 Ω cm, and high hole mobility of 10.62 cm2 V−1 s−1. Furthermore, the 4HCB (80 μm-thick film) based X-ray detectors can achieve a sensitivity of 93 μC Gyair−1 cm−2 and on/off ratio of 157. The device also shows steady flexibility, with no degradation in detecting function after 100 cycles of bending. Finally, the proposed 4HCB film detectors demonstrated a high-resolution X-ray imaging capability. The imaging of several materials with sharp edges (copper and polytetrafluoroethylene) has been obtained. This work has developed a fast but efficient approach for producing large-area, highly oriented OSC films for high-performance X-ray detectors.