Rhenium disulfide (ReS2) has recently amassed increasing interests as lithium-ion batteries (LIBs) anode material due to its extremely weak interlayer coupling and high Li storage capacity. However, its potential as high-performance sodium-ion batteries (SIBs) has rarely been explored comprehensively. In this work, we demonstrate a novel construct of ReS2 anode consisting of vertical ReS2 nanosheets uniformly grown on metal-organic framework (MOF) derived porous carbonaceous nanocubes (RESNC), is able to achieve high-performance SIBs. Exhibiting high specific surface area (117.40 m2 g−1) and near-microporous (∼2.20 nm) pore size distribution, this unique and conductive nanostructure provides abundant reactive sites which enable rapid and efficient ions/electrons transportation. For the first time, the sodiation/desodiation redox mechanisms of the ReS2-based nanostructure are revealed via ex situ investigations. Our results demonstrated that RESCN nanocomposite is endued with high capacity (365 mA h g−1, 100 mA g−1), high rate capability (up to 2 A g−1) and stable cycling performance (>600 cycles, 2 A g−1). To elaborate on the rate and cycling capabilities, various diffusion pathways of sodium-ions on the ReS2 lattice were unravelled via first-principles/ab initio techniques, with the results indicating favourable diffusion mechanics. Through the joint approach of comprehensive experimental and theoretical investigations, our results suggest that the ReS2/C composites are highly promising as high-performance SIBs anode materials, as well as broadening the current perspectives of materials choices as far as high capacity transition metal disulfides (TMDs) is concerned.