Biomass plays a fundamental role in numerous decarbonisation strategies that seek to mitigate the short- and long-term effects of climate change. Within this context, decision-makers’ choices need to comprehensively consider potential sustainability effects associated with bioenergy systems. In particular, due to the lack of studies addressing the social sustainability of bioelectricity, the present work applies the Social Life Cycle Assessment (S-LCA) methodology to compare the social performance of two biomass-to-electricity systems located in Portugal based on either fluidised-bed or grate furnace technology. S-LCA involves a comprehensive approach for holistic evaluation and data interpretation of social aspects. Six social indicators were benchmarked: child labour, forced labour, gender wage gap, women in the sectoral labour force, health expenditure, and contribution to economic development. The results show that the implementation of fluidised-bed furnaces as a more efficient conversion technology could reduce by 15–19% the selected negative social impacts, except women in the sectoral labour force. When enlarging the interpretation to a sustainability perspective, the general suitability of the fluidised-bed furnace system would be further emphasised under environmental aspects while jointly providing valuable insights for informed decision-making and sustainability reporting.