Polyhydroxyalkanoates (PHAs) are the only polyesters that are completely synthesized biologically and possess features equivalent to petroleum-based plastics besides being biodegradable. PHA based materials may certainly prove helpful in addressing the concerns caused due to the indiscriminate use of synthetic plastics. However, the cost of producing these polymers on a large scale is still uneconomical. Various approaches have been developed to tackle this issue through usage of agro-industrial wastes, co-production of high market value products, polymer extraction using green solvents, etc. The advent of recombineering and CRISPR technologies has broadened the scope of constructing a microbe capable of synthesizing multiple products with economic feasibility. Quite a few high-market value chemicals are possible to synthesize along with the favorable accumulation of PHA. The present article attempts to review all PHA polymer co-production processes with other chemicals reported till date and discusses the opportunities for their large-scale operation in future.