We show here the first radical route for the direct photosynthesis of AuCN oligomers with different sizes and shapes, as evidenced by TEM observations, from an Au nanoparticle/benzaldehyde/CH3CN ternary system in air under UV-light irradiation. This photochemical route is green, mild, and universal, which makes itself distinguishable from the common cyanidation process. Several elementary reaction steps, including the strong C-C bond dissociation of CH3CN and subsequent center dot CN radical addition to Au, have been suggested to be critical in the formation of AuCN oligomers based on the identification of center dot CN radical by in situ EPR and the radical trapping technique, and other reaction products by GC-MS and H-1 NMR, and DFT calculations. The resulting solid-state AuCN oligomers exhibit unique spectroscopic characters that may be a result of the shorter Au Au distances (namely, aurophilicity) and/or special polymer-like structures as compared with gold cyanide derivatives in the aqueous phase. The nanosized AuCN oligomers supported on mesoporous silica showed relatively good catalytic activity on the homogeneous annulation of salicylaldehyde with phenylacetylene to afford isoflavanones employing PBu3 as the cocatalyst under moderate conditions, which also serves as evidence for the successful production of AuCN oligomers.