Surface complexes formed during x3b2;-picoline transformations on V–Ti–O catalysts in the temperature range of 120–300 °C were studied using in situ FTIR spectroscopy. Two vanadia–titania catalysts with several kinds of vanadia species were used in experiments. FTIR spectra have revealed differences in composition of surface complexes under different coverage, which could be related to different ways of transformations of intermediate pyridine-3-carbaldehyde.