The glassy state of inorganic-organic hybrid metal halides combines their excellent optoelectronic properties with the outstanding processability of glass, showcasing unique application potential in solar devices, display technologies, and plastic electronics. Herein, by tailoring the organic cation from N-phenylpiperazine to dimethylamine gradually, four types of zero-dimensional antimony halides are obtained with various optical and thermal properties. The guest water molecules in crystal (N-phenylpiperazine)2SbCl6·Cl·5H2O lead to the largest distortion of the Sb-halogen unit, resulting in the red emission different from the yellow emission of other compounds. More importantly, the water molecule-induced hydrogen-bond network in (N-phenylpiperazine)2SbCl6·Cl·5H2O would prolong the relaxation time into an equilibrium state, resulting in the formation of the glassy state. This is different from the previous strategy of adopting large organic cations for glass transition. Through rheological studies, we shape an initial understanding of the underlying kinetics in inorganic-organic hybrid metal halide glass. This work provides a simpler and more convenient approach for developing inorganic-organic hybrid metal halides with superior processing performance.