We report a facile microwave-assisted green synthetic route for colloidal poly(vinyl alcohol) (PVA)-coated europium (Eu3+)-doped luminescent heavy metal bismuth oxyhalide (BiOX; X = Cl, Br, I) nanoflakes at low temperature and examine their structural, optical, and photocatalytic characteristics. PVA coating onto the surface of the nanoflakes endows them with hydrophilic nature. Both Eu3+-doped BiOCl and BiOBr nanoflakes exhibit strong optical properties related to Eu3+ and Bi3+ which are quenched in case of Eu3+-doped BiOI matrix. These results are supported by Eu3+ photoluminescence lifetime values of 0.61 ms, 0.59 ms, and 8.9 mu s, respectively. The former two matrices have quite similar crystal field environments as deduced from the asymmetric ratios of D-5(0) -> F-7(2) (614 nm) and D-5(0) -> F-7(1), (591 nm) transitions. In addition to possessing interesting photoluminescence properties, a comparison of the photocatalytic activity of Eu3+-doped BiOX (X = Cl, Br, I) nanoflakes, with corresponding estimated band gaps of 3.36, 2.74, and 1.67 eV has been evaluated using Rhodamine B (RhB) dye under visible light irradiation. The nanoflakes exhibited 100% dye degradation under visible light irradiation. Eu3+-doped BiOCl nanoflakes manifested higher photocatalytic efficiency compared to the other matrices following apparent first-order kinetics. Such a boost in efficiency is attributed to their high surface area to volume ratios, layered crystalline structures, indirect band gap nature, and ability to utilize broad bands in the solar spectrum.