X-ray photoelectron spectroscopy (XPS) is one of the main methods for elemental and bonding-state characterization in the near-surface region. Applying it as angle-resolved XPS (ARXPS), it is promising for non-destructive depth profiling in the nanometre-thickness range. The challenges for the application of ARXPS are discussed for the early film growth of Ti and Ta on SiO(2) produced by in situ magnetron sputtering. The measurements showed several phase-formation processes at the interfaces, which were used as the basis for the ARXPS data analysis and resulted in different interlayer growth information for Ti and Ta. From a systematic ARXPS data interpretation in combination with simulations, limits of the method are critically discussed.