Coffee is one of the most popular beverages in the world with an estimated 2 billion cups consumed a day. The production and consumption of coffee require extensive raw materials, energy and water, whilst generating significant spent coffee grounds (SCGs) as waste. SCGs are favourable substrates in a bio-circular-green economy being high in oil and nutrition content. Several pathways exist for the valorisation of SCGs to produce biofuels including biodiesel and biogas. The sustainability of these valorisation options is yet to be assessed. This study quantifies and compares the environmental and economic sustainability of five of the most common valorisation routes following ISO 14040-44, including life cycle assessment and life cycle costing: i) fuel pelletizing; ii) transesterification and pyrolysis; iii) pyrolysis; iv) transesterification and fermentation; and v) anaerobic digestion. The scope is from cradle-to-gate and the functional unit is “treatment of 1 tonne of SCGs”. Results indicate that fuel pelletizing has the best performance with 19 net-negative (saving) environmental impacts. Pyrolysis and anaerobic digestion are second best with 18 net-negative impacts, followed by transesterification with pyrolysis with 13 net-negative impacts. Transesterification with fermentation results in the highest environmental impacts for 16 categories, including climate change, because it has the lowest credits from co-products. For economic sustainability, all options have net-negative costs signifying they are economically feasible. This study also applies Multi-Criteria Decision Analysis to determine the best valorisation routes based on environmental and economic aspects. Pyrolysis is found to be the most sustainable route, followed by fuel pelletizing, transesterification with pyrolysis, and anaerobic digestion. Transesterification with fermentation, conversely, is found to be the least sustainable option. These results will be of interest to coffee producers, policy makers, and other stakeholders looking to improve the sustainability of the coffee industry.