The multiphoton ionization of the hydrogen-bonded clusters N,N-dimethylformamide-(methanol) n (DMF-(CH 3 OH) n ) was studied using a time-of-flight mass spectrometer at the wavelengths of 355 and 532 nm. At both wavelengths, a series of protonated DMF-(CH 3 OH) n H + ions was obtained. The clusters were also investigated by density functional theory B3LYP method in conjunction with basis sets 6-31+G(d,p) and 6-311+G(2d,p). Equilibrium geometries of both neutral and ionic DMF-CH 3 OH clusters, and dissociation channels and dissociation energies of the ionic clusters are presented. The results show that when DMF-CH 3 OH is vertically ionized and dissociated, DMFH + and CH 3 O are the dominant products via proton transfer reaction. A high energy barrier makes another channel corresponding to the production of DMFH + and CH 2 OH disfavored. In the DMF-(CH 3 OH)H + ion, the proton prefers to link with the O atom of DMF molecule. Variation of atomic charges during proton transfer in hydrogen bond of the protonated cluster DMF-(CH 3 OH)H + ion is also discussed.