Anoxygenic purple phototrophic bacteria (PPB) were utilised in an 80 L biofilm flat plate photobioreactor to generate polyhydroxyalkanoate (PHA) over 44 cycles, with acetate as feed. Over the cycles, net PHA yield (growth + accumulation) averaged 21% while accumulation yield averaged 55%. Average PHA content was 35 wt% volatile solids (VS), with the majority (>80%) being harvested from the biofilm at 100 gTotal solids (TS) L⁻¹. The PPB microbial population averaged 45% of total population. Detailed cycle studies indicated that PHA content (and yield) peaked at 0.5–1 d into the accumulation stage (peak of 53 wt% VS), suggesting that cycle time optimisation could improve both yield and selection of PHA accumulators. The resulting polymeric material was comprised of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with 95.5 mol% 3-hydroxybutyrate and 4.5 mol% 3-hydroxyvalerate content, but the molecular weight, at >1090 kDa, is unusually high for extracted, microbially produced PHA and a feature of this work.