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SnS is an important semiconductor and its performance depends greatly on its morphology and 3D architecture. So the synthesis for it with specific structures has been widely paid attention. Herein, a novel hollow nanoparticle-based SnS crystal product with microcluster-like 3D network hierarchitectures was developed, via a template-assisted solvothermal route in diethylene glycol (DEG) solvent, followed by annealing in N 2 atmosphere and subsequent corrosion of template by dilute acid. CaCO 3 nanoparticles were used as the template, SnCl 2 as the tin source, thiourea and l -cysteine hydrochloride monohydrate (Cys) as two different sulfur sources for a comparison study. Results show that successful fabrication of the hollow-structured SnS product mentioned above was achieved only in the case of using Cys as the sulfur source, mainly due to much stronger adhesion of Cys on CaCO 3 template and microcluster-like stacking patterns of CaCO 3 nanoparticles in DEG solvent. This novel 3D hierarchical SnS product owns 1–5 times higher specific surface area, unique hollow nanostructure units with rich mesopores inside the shells, and scattering-enhanced absorption in UV–vis light region, as against those previously reported micro-scale tin sulfide 3D hierarchitectures assembled by nanopetals, nanosheets, nanorods, nanobelts, etc. So it should have much more extensive and promising applications. [ABSTRACT FROM AUTHOR]