This study evaluated the influence of different carbon sources on purple non-sulphur bacteria (PNSB) biofilm formation, and the production of polyhydroxybutyrate (PHB) and other value-added bio-products. Higher PNSB growth and biofilm formation were observed in fuel-synthesis wastewater (FSW), followed by acetate. Both FSW and acetate cultures contained a large proportion of Rhizobiales, while sugar substrates led to yeast enrichment. Protein contents reached 40–41 % for acetate, which is suitable for single cell protein (SCP) use. The maximum PHB content from the suspended and biofilm growth was obtained from glucose (18.1 ± 0.10 %, 12.9 ± 1.11 %), followed by FSW (14.9 ± 0.25 %, 11.2 ± 0.50 %). FSW showed the highest overall productivity for both protein and PHB. Pigment concentrations were low for all substrates. The study underscores substrate influence on microbial community and bioproducts potential. It highlights FSW as a promising substrate for PNSB, suggesting its treatment integration for resource recovery.