We studied the influence of changing the degree of fluorination in eight new gold(i) derivatives containing both JohnPhos phosphine and polyfluorinated thiolates: [Au(SRF)(JPhos)], JPhos = P(C6H4-C6H5)(t-But)2 and RF = C6F5 (1), C6HF4 (2), C6H3F2-3,5 (3), C6H3F2-2,4 (4), C6H4F-2 (5), C6H4F-3 (6), C6H4F-4 (7) and CF3 (8). We determined the molecular and crystal structures of all new compounds by single crystal X-ray diffraction. Later, we characterised the chemical bonding scenario with quantum chemical topology tools, specifically the Quantum Theory of Atoms in Molecules (QTAIM) and the analysis of the NCI-index. Our QTAIM results indicate that while the linear S-Au-P moiety is unaffected by the variation of the fluorine content on the thiolates and that Au-S and Au-P bond strengths are mostly constant for all compounds in the series, the π character of gold bonds seems to be modified by the fluorination of the substituents at the thiolate ligand. Besides, the examination of the NCI-index reveals the presence of weak Au-πPhenyl non-covalent interactions in all compounds. Overall, this study shows the relevance of (i) the π-backbonding properties of the metal centre and (ii) different non-covalent interactions in the stability of JohnPhos gold(i) compounds.