Low-dose X-rays in the order of milligrays (mGy) are employed in diagnostic radiology. This poses a challenge, considering commercially used dosimeters have limitations in detecting low-dose X-rays. Accordingly, the goal of this research was to fabricate a nitro blue tetrazolium-doped polyvinyl alcohol (PVA/NBT) film dosimeter that could respond to low-dose X-rays while also investigating the effects of introducing copper(II) and bismuth(III) ions on the film's detecting ability. The films were synthesized by the solvent casting method and then exposed to X-ray radiation at doses in the range of 0–2.626 mGy. Optical density and UV–Vis transmittance measurements were carried out to identify changes in the film's optical characteristics brought on by X-ray radiation. In addition, changes in the film's surface morphology and chemical structure were examined by scanning electron microscopy (SEM) and FTIR spectroscopy. According to the results of the optical density measurement, introducing copper(II) ions to the film increased its sensitivity and response linearity. In contrast, the opposite was shown in the case of bismuth(III)-doped films. According to FTIR analysis, film X-ray irradiation caused the PVA to degrade. The development of grain structures on the film surface might be related to the reduction of the copper(II) and bismuth(III) ions. This study discovered that copper(II) ion-doped PVA/NBT film has promising low-dose X-ray detection properties.