The generation of municipal solid waste (MSW) is increasing globally every year, including in Malaysia. Approaching the year 2020, Malaysia still has MSW disposal issues since most waste goes to landfills rather than being utilized as energy. Process network synthesis (PNS) is a tool to optimize the conversion technologies of MSW. This study optimizes MSW conversion technologies using a PNS tool, the “process graph” (P-graph). The four highest compositions (i.e., food waste, agriculture waste, paper, and plastics) of MSW generated in Malaysia were optimized using a P-graph. Two types of conversion technologies were considered, biological conversion (anaerobic digestion) and thermal conversion (pyrolysis and incinerator), since limited data were available for use as optimization input. All these conversion technologies were compared with the standard method used: landfilling. One hundred feasible structure were generated using a P-graph. Two feasible structures were selected from nine, based on the maximum economic performance and minimal environmental impact. Feasible structure 9 was appointed as the design with the maximum economic performance (MYR 6.65 billion per annum) and feasible structure 7 as the design with the minimal environmental impact (89,600 m3/year of greenhouse gas emission).