The characteristics of mechanical flexibility, low health risk, and simple processing of polymer nanocomposite materials make them potentially applicable as flexible X-ray detectors. In this study, we report on a high sensitivity, environmentally friendly, and flexible direct X-ray detector using polymer nanocomposite material consisting of bismuth oxide (Bi2O3) nanoparticles and polydimethylsiloxane (PDMS). This detector was realized by printing patterned Ag electrodes on the polymer nanocomposite material. The response of PDMS to X-rays was verified for the first time, and the effect of doping different contents of Bi2O3 nanoparticles on the performance of the device was tested. The optoelectronic performance of the optimized detector indicated a high sensitivity (203.58 μC Gyair−1 cm−2) to low dose rate (23.90 μGyair s−1) at a 150 V bias voltage and the X-ray current density (JX-ray) was 10,000-fold higher than the dark current density (Jdark). The flexible direct X-ray detector could be curled for 10,000 cycles with slight performance degradation. The device exhibited outstanding stability after storage for over one month in air. Finally, this device provides new guidance for the design of high-performance flexible direct X-ray detectors.