The reactions of metal cluster ions, M-n(+), with water and alcohols, where M+ is calcium (n = 1-7), strontium (n = 1-6), or barium (n = 1-4), have been studied using a pulsed arc cluster ion source (PACIS) in association with a Finnigan ion trap. The dominant reaction products with water are found to have the general formula M-n(+)(OH)(2n-1), which can be attributed to M+OH in association with (n - 1) neutral M(OH)(2) species. Other products present in the trap include Mn+Op(OH)(q) cluster ions covering a range of values for n, p, and q. A few M-n(+)(OH)(2n-1), and Mn+Op(OH)(m) ions respond to collisional activation, but the majority of complexes are found to be reluctant to fragmentation. The reactions of individual Mn+(OH)(2n-1) complexes have been studied in the presence of methanol, ethanol, and 1-propanol, and the results have been interpreted in terms of the sequential exchange of hydroxyl groups for MeO, EtO, and PrO, respectively. A general formula for these reactions is proposed to be M-n(+)(OH)(2n-1) + m(ROH) --> M-n(+)(OH)(2n-m-1)(RO)(m) + m(H2O), where ROH is the alcohol, the final products being M-n(+)(MeO)(2n-1), M-n(+)(EtO)(2n-1), and M-n(+)(PrO)(2n-1). Supporting calculations suggest possible candidate structures for two of the M-n(+)(OH)(2n-1) ions; however, neither provides an obvious route to the complete exchange of OH for OR.