The aim of this study was to evaluate an effect of short and medium chain carboxylic acids (CAs) rich stream derived from acidogenic mixed culture fermentation of acid whey on polyhydroxyalkanoates (PHAs) synthesis by Paracoccus homiensis and compare it with the impact of individual synthetic CAs. The obtained results confirmed that the analyzed bacterium is able to metabolize synthetic CAs as the only carbon sources in the growth medium with maximum PHAs production yields of 26% of cell dry mass (CDM). The replacement of the individual CAs by a CAs-rich residual stream was found to be beneficial for the Paracoccus homiensis growth. The highest biomass concentration reached about 2.5 g/L with PHAs content of 17% of CDM. The purified PHAs were identified as poly(3-hydroxybutyrate-co-3-hydroxyvalerate) by applying gas chromatography coupled with mass spectrometry, Fourier transform infrared spectroscopic spectra and UV-Vis spectra. Furthermore, a differential scanning calorimetric, thermogravimetric and water contact angle analysis proved that the extracted copolymers have useful properties. The obtained data are promising in the perspective of developing a microbial PHAs production as a part of an integrated valorization process of high CAs content waste-derived streams.