A synthesis of novel crystalline stibnite (Sb2S3) submicrometer-sized rod bundles of straw has been investigated using a wet chemical method via thermal decomposition of an antimony(Ill) diethyldithiocarbamate complex in ethylene glycol under mild conditions. By carefully controlling the experimental parameters, such as precursor concentration, temperature, and time, flowerlike bunches of rods and straw-shaped crystalline stibnite submicrometer-sized rod bundles are successfully achieved. The possible mechanism is proposed, which reveals that the inherent highly anisotropic layered structure of stibnite and precursor concentration take crucial roles in determining the final morphologies of the products. The high yields, simple reaction apparatus, low manipulating temperature, and newly discovered uniform morphology of the products may mean that this simple method has good potential in related future applications.