Binding of gold clusters with adenine was studied using density functional method (DFT). Geometries of neutral adenine with Au(n) (n = 2, 3 and 4) clusters were optimized using the B3LYP approach. The 6-31G+(d, p) basis set was used for adenine and the Stuttgart/Dresden effective core potential (ECP) basis set SDD was employed for the gold atom. Structural parameters and energy properties were discussed for the optimized complexes stabilized with the anchoring Au-N and the nonconventional Au...H-N hydrogen bond. The calculated interacting energy results show that the binding of Au(n) is the most strong at N3, whereas its binding at N6 displays relatively weaker stability. Furthermore, analysis of the charge distributions of the optimized complexes by using the natural bond orbital analysis indicates charge is transferred from the lone pair of nitrogen in adenine to the n* and sigma* orbitals of Au during the interaction between the Au(n) and adenine. The calculated second-order perturbation stabilization energies show that the interaction Au-N anchoring bond plays an important role compared with the nonconventional Au...H-N hydrogen bond.