Uniform 3D flower-like β-In2S3 microstructures were synthesized using InCl3·4H2O and KSCN as starting reagents in ethylene glycol at 200-220°C for 30h under solvothermal conditions. The prepared products were characterized by various techniques, such as XRD, XPS, FESEM, TEM and ED. FESEM and TEM observation reveals that the as-prepared flower-like β-In2S3 microstructures are assembled by plate-like nanocrystals with average thickness of 10nm. These nanoplates interconnect with each other to form an entangled network-like architecture with irregular-shaped pore in the flower-like β-In2S3 microstructures. Photoluminescence (PL) spectrum indicates that the synthesized β-In2S3 porous micro spheres have shown considerably greater quantum size effects.