Owing to the exterior self-trapped excitons (STEs) with adjustable fluorescence beams, low-dimensional ns2-metal halides have recently received considerable attention in solid-state light-emitting applications. However, the photoluminescence (PL) mechanism in metal halides remains a major challenge in achieving high efficiency and controllable PL properties because the excited-state energy of ns2 conformational ions varies inhomogeneously with their coordination environments. Here, a novel zero-dimensional (0D) lead-free bismuth-based Rb3BiCl6·0.5H2O crystal was reported as a pristine crystal to modulate the optical properties. By doping Sb3+ ions with 5s2 electrons into Rb3BiCl6·0.5H2O crystals, bright orange emission at room temperature was obtained with a photoluminescence quantum yield of 39.7%. Optical characterizations and theoretical studies show that the Sb3+ doping can suppress the strong exciton-phonon coupling, optimize the electronic energy band structure, improve the thermal activation energy, soften the structural lattice of the host crystals, deepen the STE states, and ultimately lead to strong photoluminescence. This work manifests a fruitful manipulation in ripening bismuth-based halides with high-efficiency PL properties, and the PL enhancement mechanisms will guide future research in the exploration of emerging luminescent materials.