Technical Abstract: Bioblends are composites of at least one biodegradable polymer with non-biodegradable polymer. Successful development of bioblends requires that the biodegradable polymers be compatible with other component polymers. Compatibility can be assessed by evaluating the intermolecular interactions between the component polymers. In this work, the interaction in binary bioblends comprising biodegradable poly-lactic acid (PLA) and polystyrene (PS) was investigated using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and Fourier transform infrared photoacoustic spectroscopy (FTIR-PAS). The TGA studies indicated that incorporation of PLA in PS resulted in thermal destabilization of PS. The DSC studies showed that some parameters favored partial miscibility of PS in PLA, while others favored immiscibility, such as the existence of two glass transitions. The FTIR-PAS spectra revealed the presence of intermolecular n-Pi interactions between PLA and PS and indicated the degree of interaction was dependent on the concentrations of the polymers in the bioblends. FTIR-PAS results computed via differential spectral deconvolution were consistent with, and therefore support, the results of TGA and DSC analyses of PLA/PS bioblends. The degradation kinetics, used to determine degradation mechanism, revealed two or three steps mechanism.