A new strategy was explored to generate pure gold cluster ions, Au(n)(+/-), from gold films deposited on solid substrates via a matrix-assisted laser ablation technique. The gold films deposited on SiO(2)-particle-assembled photonic crystals were demonstrated to be the most ideal compared with the films deposited on various glass slides. Dropped with a matrix of 2-(4-hydroxyphenylazo) benzoic acid and bombarded by nitrogen pulse laser (355 nm), they could release a series of Au(n)(+) with n more than 110 or Au(n)(-) with n more than 60 according to the data obtained by inline time-of-flight mass spectrometry. The gold-deposited photonic crystal substrates could be stored at room temperature for at least 6 months. The method is hence steady and convenient in use.