We have investigated the electronic structure of BaBiO3 and BaY0.1Bi0.9O3 using x-ray photoemission spectroscopy techniques. The valence band spectrum obtained from XPS, shows an increase in the band gap of BaY0.1Bi0.9O3 when compared with BaBiO3. Resistivity data collected for the two samples show that the resistivity increases when BaBiO3 is doped with Yttrium. The core levels collected indicate a shift in the peaks in BaY0.1Bi0.9O3 towards lower binding energy. Interestingly, the valence band studies reveal weak structures in BaBiO3 in the energy range of 0.5 eV to 2.5 eV, on Y-doping are strongly suppressed. We intend to study this phenomenon further in order to understand the effects of doping and perceive its origin.