The first example of a homogeneous hydration of aromatic nitriles catalyzed by manganese molecular compounds is reported. The Mn(I) organometallics fac-[(CO)3Mn(dippe)(Z)]1-nX1-n (n = 0, 1; Z = Br, OTf, PhCN; X = OTf) were synthesized and characterized, and their reactivity was studied. Species fac-[(CO)3Mn(dippe)(OTf)] (2) was used as a catalyst precursor for the selective hydration of benchmark benzonitrile (2 mol% 2, THF/H2O 1:2v/v, 18 h, 100 ºC) to produce benzamide in 90% isolated yield. A series of (hetero)aromatic nitriles were hydrated to synthesize the corresponding amides in very good to excellent yields (88-94%). Isotopic labeling studies accounted for a proton transfer as the rate determining step.