Poly-hydroxyalkanoates are an example of biodegradable and biocompatible polymers, produced from renewable raw materials. With respect to other bioplastics the market share of poly-hydroxyalkanoates is still limited because of their commercial costs. To develop more cost-effective processes, a multilevel approach is usually undertaken combining innovative, cheaper and more effective microbial cultivation with safe and cheap extraction and purification methodologies. This study assesses the potential life cycle environmental impacts related to a novel protocol poly-hydroxyalkanoates extraction based on dimethyl carbonate in comparison to the use of halogenated hydrocarbons (in particular 1,2 dicholoroethane). Four scenarios are analysed for the dimethyl carbonate protocol considering: extraction from microbial slurry or from dried biomass, and recovery by solvent evaporation or polymer precipitation. The life cycle assessment demonstrates that the environmental performances of dimethyl carbonate-based protocols are far better than those of the most comparative process using the halogenated hydrocarbons. The scenario that foresees the extraction of dried biomass and recovers solvent by evaporation appears to be the most promising in terms of environmental sustainability performance.