Aluminum-sulfur cluster ions were obtained by direct laser ablation (248 nm, greater than or equal to 10 MW/cm(2)) and analyzed with a tandem time-of-flight mass spectrometer. The regular peaks of cluster ions having composition of AlS+(Al2S3)(n) (n=1,2,3,...,31) were shown on the first time-of-flight mass spectrum (TOF-MS). The cluster ions of a certain mass number (m/e) could be selected and photolyzed by an ArF laser (193 nm, 1 MW/cm(2)). The product ions were analyzed by a second TOF-MS. It was found that the cluster ions lost (Al2S3)(x) (x = 1, 3, or 4) and became smaller cluster ions of the same stable formula AlS+(Al2S3)(n-x). Cagelike structures were proposed to be possible for these stable cluster ions. Semiempirical and ab initio quantum chemical calculations have also been performed for some of the clusters.