Highly flexible composite films based on bacterial cellulose, glycerol and polyvinyl alcohol (PVOH) with UV barrier properties were developed. The open nanoscale network of bacterial cellulose allowed to combine it with glycerol and polyvinyl alcohol by immersion. This procedure kept intact the bacterial cellulose structure. The interactions among bacterial cellulose, glycerol and PVOH were analyzed using scanning electron microscopy, infrared spectroscopy, thermogravimetry and differential scanning calorimetry. In general, the addition of PVOH reinforced the bacterial cellulose matrix, meanwhile glycerol showed a significant plasticizing effect. Formulations with PVOH and glycerol reached a maximum value of 49.89% of elongation and a good resistance to rupture of 13.78 MPa. The water vapour permeability ranged from 1.87·10−11 to 2.04·10−10 g/m s Pa. The UV-VIS spectral analysis showed that glycerol decreased the transmittance in the UV area and polyvinyl alcohol enhanced the transparency values of the samples in the VIS region. The transmittance in the UV-A, UV-B and UV-C areas for films based on bacterial cellulose with glycerol reached up to 5.59, 2.4 and 0.57%, respectively.