The huge amount of biomass waste and palm oil mill effluent (POME) generated during oil extraction has prompted the need for a more sustainable framework in waste management. Since oil palm biomass waste is rich in lignocellulosic content, it can be potential to be converted into green energy such as bioelectricity via different pathway of processes such as the thermal conversion pathway and biochemical conversion pathway. This study proposes a mathematical approach to synthesise a sustainable supply chain of biomass to electricity by implementing the combined heat and power (CHP) system in palm oil mill. The optimum pathway of supply chain based on the technical, economical, and environmental aspects is generated. The purpose of this approach is to assists the industry players or owners to make decision in choosing the location of the pre-treatment technology, transportation method, location of power plant and configuration of CHP. A generic superstructure is first developed to achieve the objective. Then, a series of generic mathematical equations will then be formulated based on the pathways demonstrated in the generic superstructure. The mathematical equations involve general mass and energy balance, cost computation and carbon emission. The fuzzy optimisation concept will be adopted in this research to trade-off the conflicting objectives (maximize profit and minimize carbon footprint) in order to generate the optimum pathway. A palm oil-based bioelectricity supply chain case study in Selangor, Malaysia is solved to illustrate the presented approach. According to the optimised result in this case study, a total of 3,753.36 MW of bioelectricity can be generated per year. The result proved that the optimum pathway is feasible by comparing with the existing oil palm biomass-based power plant in Sarawak, where only 375 MW of electricity is generated by oil palm biomass. On the other hand, RM 7.25 million per year of net profit is estimated with a payback period of 2.81 years. Moreover, the CHP system is able to achieve 570 million kg CO2 per year.