We report on a comprehensive analysis of titanium boride thin films by x-ray photoelectron spectroscopy (XPS). Films were grown by both direct current magnetron sputtering and high- power impulse magnetron sputtering from a compound TiB2 target in Ar discharge. By varying the deposition parameters, the film composition could be tuned over the wide range 1:3 &B/Ti &3:0, as determined by elastic recoil detection analysis and Rutherford backscattering spectrometry. By comparing spectra over this wide range of compositions, we can draw original conclusions about how to interpret XPS spectra of TiBx. By careful spectra deconvolution, the signals from Ti-Ti and B-B bonds can be resolved from those corresponding to stoichiometric TiB2. The intensities of the off-stoichiometric signals can be directly related to the B/Ti ratio of the films. Furthermore, we demonstrate a way to obtain consistent and quantum-mechanically accurate peak deconvolution of the whole Ti 2p envelope, including the plasmons, for both oxidized and sputter-cleaned samples. Due to preferential sputtering of Ti over B, the film B/Ti ratio is best determined without sputter etching of the sample surface. This allows accurate compositional determination, assuming that extensive levels of oxygen are not present in the sample. Fully dense films can be accurately quantified for at least a year after deposition, while underdense samples do not give reliable data if the O/Ti ratio on the unsputtered surface is *3:5. Titanium suboxides detected after sputter etching is further indicative of oxygen penetrating the sample, and quantification by XPS should not be trusted.