The synthesis of four novel gold(i)-phosphane complexes coordinated to 9-phenanthrene chromophore has been carried out through the reaction of 9-phenanthreneboronic acid and the corresponding AuClPR3 (PR3 = PPh3 for triphenylphosphane (1a); 1,4-bis(diphenylphosphanyl)butane or dppb (2b); bis(diphenylphosphanyl)acetylene or dppa (2c); (AuCl)2(diphos) (diphos = bis(diphenylphosphanyl)methane or dppm (3)) sources. The X-ray crystal structures of compounds 1a and 2b show the existence of MOF-like intermolecular assemblies that contain empty inner cavities in the absence of aurophilic contacts. In contrast, the formation of a tetranuclear complex with intramolecular aurophilic interactions was evidenced for 3. Photophysical characterization indicates dual emission in all gold(i) complexes when oxygen is removed from the sample, while only fluorescence emission is recorded for the uncoordinated ligand. The introduction of the compounds within PMMA and Zeonex was assayed, and luminescent films containing gold(i) complexes where phosphorescence is the sole pathway for emission are obtained, instead of the dual emission (with significant fluorescence contribution) recorded in solution.