Coconut-like monocrystalline SnS/C nanospheres are developed as anode materials for lithium-ion batteries by a micro-evaporation-plating strategy in confined nanospaces, achieving reversible capacities as high as 936 mAhg(-1) at 0.1 Ag-1 after 50 cycles and 830 mAhg(-1) at 0.5 Ag-1 for another 250 cycles. The remarkably improved electrochemical performances can be mainly attributed to their unique structural features, which can perfectly combine the advantages of the face-to-face contact of core/shell nanostructure and enough internal void space of yolk/shell nanostructure, and therefore well-addressing the pivotal issues related to SnS low conductivity, sluggish reaction kinetics, and serious structure pulverization during the lithiation/delithiation process. The evolutionary process of the nanospheres is clearly elucidated based on experimental results and a multiscale kinetic simulation combining the microscopic reaction-diffusion equation and the mesoscopic theory of crystal growth. Furthermore, a LiMn2O4//SnS/C full cell is assembled, likewise exhibiting excellent electrochemical performance. (c) 2018 American Institute of Chemical Engineers AIChE J, 64: 1965-1974, 2018