Developing non-toxic, semiconductor-doped heterojunction materials for optoelectronic applications on the surface of a flexible substrate is a viable strategy for meeting the world’s energy needs without introducing any environmental issues. In this paper, Ti:TiO2/ZnO nanocomposites were prepared by heat treatment and utilized as an active layer in UV photodetectors. First, a ZnO seed layer was deposited by radio frequency (RF) sputtering on polytetrafluoroethylene (PTFE) substrates. Then, TiO2/ZnO thin films (TFs) were successfully grown by combining volumetric mixtures of TiO2 and ZnO at the ratios of 1:7, 1:3, 3:5, and 1:1 via the chemical bath deposition (CBD) method. The morphological, elemental, and topographical analyses of the grown TFs were investigated through SESEM, EDX, and AFM spectroscopy, respectively. XRD patterns illustrated the presence of the unified (002) peak of the Ti/ZnO hexagonal wurtzite structure in all prepared samples, with intensities indicating a very strong preferential crystallinity with increasing TiO2 ratios. Enhanced diffuse reflectance curves were obtained by UV–Vis spectroscopy, with allowed indirect energy bandgaps ranging from 3.17 eV to 3.23 eV. FTIR characterization revealed wider phonon vibration ranges indicating the presence of Ti–O and Zn–O bonds. Metal–semiconductor–metal (MSM) UV photodetectors were fabricated by thermally evaporating Ag electrodes on the grown nanocomposites. The volumetric ratio of TiO2/ZnO impacted the photodetector performance, where the responsivity, photosensitivity, gain, detectivity, rise time, and decay time of 0.495 AW−1, 247.14%, 3.47, 3.68 × 108 jones, 0.63 s, and 0.99 s, respectively, were recorded at a ratio of 1:1 (TiO2:ZnO). Based on the results, the heterostructure nanocomposites grown on PTFE substrates are believed to be highly promising TF for flexible electronics.