Preparation of shape-controlled metastable gamma-MnS semiconductor nanocrystals has been achieved on a large scale through a simple solvothermal method in the presence of PVP. The key strategy is the use of sulfur powder as sulfur source in ethylene glycol (EG) solvent that also acted as a weak reducing agent. Reaction parameters such as reaction time and temperature are found to be important in controlling various hierarchical architectures, such as homogeneous semi-hollow core-shell, hollow nanospheres, and nanowires. Transmission electron microscopy observations indicate that these hierarchical architectures are formed mainly via Ostwald ripening. The optical absorption measurements reveal that these novel architectures exhibit remarkable shift of absorption peak during the course of structural compaction and grain growth.