Forming colloidal solutions containing semiconductor quantum-sized nanoparticles (NPs) with clean surface has been a long-standing scientific challenge. In this contribution, we report a “top-down” method for the fabrication of Ge NPs by laser ablation of a Ge target in deionized water without adding any stabilizing reagents. The initial Ge NPs in amorphous structure showed spontaneous growth behavior by aging Ge colloids in deionized water under ambient temperature, which gradually evolved into a metastable tetragonal structure as an intermediate phase and then transformed into the stable cubic structure, being consistent with the Ostwald's rule of stages for the growth in a metastable system. The laser-induced initial Ge NPs demonstrate a unique and prominent size-dependent chemical reductive ability, which is evidenced by the rapid degradation of organic molecules such as chlorinated aromatic compounds, organic dyes, and reduction of heavy metal Cr(VI) ions.