This study investigates the environmental and energy performance of rice straw-based energy pathways in Egypt, combining life cycle assessment (LCA) with supply chain optimization to improve system efficiency. The analysis covers thirteen governorates producing over 4.45 million tons of rice straw annually. It examines the whole supply chain from paddy farming, straw collection, and transport to electricity generation and ash disposal. Total energy consumption was 11,287 TJ, dominated by farming (5673 TJ) and transport (5490 TJ). Greenhouse gas (GHG) emissions were estimated at 12,007.5 million kg CO2-eq, with significant contributions from farming (5158 million), combustion (3630 million), and natural gas use (3039 million). Gross electricity output was 5525 GWh, yielding a net of 4973 GWh, equivalent to 1116.5 kWh per ton of straw. Scenario analysis highlighted that the optimized multi-hub system, prioritizing Cluster 1 in the Nile Delta, which contributes over 92% of straw production and 4607 GWh of net electricity, achieved a reduction of more than 25% in transport distances and an 18% decrease in diesel consumption and related emissions. Sensitivity analysis further indicated that delivered electricity and GHG intensity are more sensitive to conversion efficiency and transmission and distribution losses than to moderate changes in transport assumptions. In addition to environmental improvements, the optimized scenario indicates potential social co-benefits, including rural employment generation, additional income opportunities for farmers, and improved air quality associated with reduced open-field burning. These outcomes are presented as indicative qualitative insights. Findings confirm rice straw as a strategic, scalable, and sustainable energy resource aligned with Egypt’s Vision 2030 and the UN Sustainable Development Goals (SDGs).