Zero-dimensional (0D) metal halide hybrids incorporating optically emissive Sb3+ dopants have received huge research attention as a result of dopant-based visible emission for lighting and scintillation applications. Indeed, there have been a plethora of reports on Sb3+ doping of indium halide (In-X)-based 0D hybrids that show strong dopant emission with varied emission wavelengths (λem) and photoluminescence quantum yields (PLQYs). However, discerning the structure-luminescence relation in these 0D-doped hybrids remains challenging because it necessitates exquisite synthetic control on the local metal (dopant) halide geometry/site asymmetry. Demonstrated here is synthetic control that allows tuning of the local metal halide geometry of the Sb3+ dopants in 0D In-X hybrids utilizing five different organic cations. Experimental analysis of the series of Sb3+-doped In-X hybrids reveals a strong correlation between the extent of local metal halide geometry distortion and their photophysical properties (λem and PLQY). Density functional theory calculations of the doped compounds, characterizing ground- and excited-state structural distortions and energetics, reveal the origin of the extent of luminescence behavior. The experimental-computational results reported herein unravel the operative structure-luminescence relation in 0D Sb3+-doped In-X hybrids, provide insight into the emission mechanism, and open up avenues toward rational synthesis of strongly emissive materials with desired emission color for targeted applications.