Leachate from the source separated organic fraction of municipal solid waste (OFMSW) was evaluated as a substrate for polyhydroxyalkanoates (PHA) production. Initially, the enrichment step was conducted directly on leachate in a feast-famine regime. Maximization of the cellular PHA content of the enriched biomass yielded to low PHA content (29 wt%), suggesting that the selection for PHA-producers was unsuccessful. When the substrate for the enrichment was switched to a synthetic volatile fatty acid (VFA) mixture -resembling the VFA carbon composition of the leachate-the PHA-producers gained the competitive advantage and dominated. Subsequent accumulation with leachate in nutrient excess conditions resulted in a maximum PHA content of 78 wt%. Based on the experimental results, enriching a PHA-producing community in a “clean” VFA stream, and then accumulating PHA from a stream that does not allow for enrichment but does enable a high cellular PHA content, such as OFMSW leachate, makes the overall process much more economically attractive. The estimated overall process yield can be increased four-fold, in comparison to direct use of the complex matrix for both enrichment and accumulation.