Display omitted •A series of novel metal-selenide/MXene composites are designed for Li/Na storage.•These composites with MXene supporting framework are rich in meso- and macropores.•A selenium-vacancy rich CoSe2@C/MXene composite is synthesized by ball-milling.•This avoids critical preparation and storage condition for few-layered MXenes.•The process reported shows a much lower environmental footprint and energy cost. The development of new energy-related materials is the pinnacle to attaining a sustainable society based on renewable energy. Over the past decades, plenty of electrode materials have been investigated seeking better energy storage properties. However, the often-tedious synthetic procedures and large amounts of solvents utilised during their syntheses incur high costs and severe environmental pollution. Here we present a solvent-free approach to metal–organic-frameworks/MXene-derived carbonaceous metal selenide/MXene composites with unique nanostructures rich in mesopores and macropores. These species can be readily transformed into high-performance electrode materials with enhanced Li/Na ion storage properties compared with their solution-based counterparts. Herein we report not only a unique metal–organic framework/MXene-derived electrode material displaying high-performance for advanced lithium/sodium storage applications but also its novel environmentally benign production process.