A series of Au(III) complexes bearing arylphosphine oxide ligands with systematically varied aromatic linkers (conjugate to fused: phenyl, biphenyl, naphthyl, anthracenyl) were synthesized via a Suzuki-Miyaura cross-coupling procedure. Their structures were confirmed by spectroscopic methods and single crystal X-ray diffraction (XRD) analysis. Photophysical studies revealed that the nature of the aromatic linker is a key factor in tuning the emission properties. While complexes with phenyl and biphenyl linkers display phosphorescence from the cyclometalating CNC (CNC = 2,6-diphenylpyridine) ligand, the naphthyl-based analogue exhibits unique dual phosphorescence, originating from two near-lying triplet states localized on the CNC and naphthyl fragments, respectively. In contrast, the anthracenyl-based complex shows ligand-centered fluorescence in solution and dual emission in the solid state. The nature of the electronic transitions responsible for absorption and emission was assigned based on a detailed analysis of DFT calculations.