This study investigates alginate-chitosan polyelectrolyte complexes (PECs) in the form of a film, a precipitate, as well as a layer-by-layer (LbL) assembly. The focus of this study is to fully characterize, using the complementary techniques of Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) in combination with solution stability evaluation, the interactions between alginate and chitosan in the PECs. In the FTIR spectra, no significant change in the band position of the two carbonyl vibrations from alginate occurs upon interaction with different ionic species. However, protonation of the carboxylate group causes a new band to appear at 1710 cm(-1), as anticipated. Partial protonation of the amine group of chitosan causes the appearance of one new band (similar to 1530 cm(-1)) due to one of the -NH3+ vibrational modes (the other mode overlaps the amide I band). Importantly, the position of the two main bands in the spectral region of interest in partly protonated chitosan films is not dependent on the extent of protonation. XPS N 1s narrow scans can, however, be used to assess the degree of amine protonation. In our alginate-chitosan film, precipitate, and LbL assembly, the bands observed in the FTIR correspond to the species -COO- and -NH3+, but their position is not different from each of the single components. Thus, the conclusion of the study is that FTIR cannot be used directly to identify the presence of PECs. However, in combination with XPS (survey and narrow N 1s scans) and solution stability evaluation, a more complete description of the structure can be obtained. This conclusion challenges the assignment of FTIR spectra in the literature.