Thin films of interstitial boron-doped anatase TiO2, with varying B concentrations, were deposited via one-step atmospheric pressure chemical vapour deposition (APCVD) on float glass substrates. The doped films showed a remarkable morphology and enhanced photoactivity when compared to their undoped analogues. The TiO2:B films also presented enhanced conductivity and electron mobility as measured by Hall Effect probe as well as a high adherence to the substrate, stability and extended lifetime. The structure and composition of the different samples of TiO2:B films were studied by X-ray Diffraction (XRD), Raman spectroscopy, Scanning Electron Microscopy (SEM) and Dynamic Secondary Ion Mass Spectrometry (D-SIMS). Hybrid density functional theory was used to explore the defect chemistry of B-doped anatase and to understand the experimental results.