Atomically precise, quantum-sized gold nanoclusters (NCs) exhibit interesting photoluminescence (PL) properties because of their quantized electronic energy levels and semiconductor nature. Among several parameters, the surface motifs play a crucial role in controlling the PL properties of the gold NCs. Here, a series of Au 36 (SR) 24 NCs with varying ligand bulkiness at the para-position of benzenethiolates are synthesized and their PL properties are explored. Detailed photophysical studies revealed that the PL quantum yield (QY) of these NCs can be tailored by tuning the ligand bulkiness. Moreover, the single-crystal X-ray diffraction (SCXRD) comparison of the structural patterns and interligand interactions in these Au 36 (SR) 24 NCs helped in the comprehension of the photophysical properties in a superior way. Overall, this work provides interesting insights into custom tailoring the structure of atomically precise NCs to find applications in these potential fields.