The infrared photodissociation spectrum of the CH3CNH+-H-2 complex has been recorded in the vicinity of the H-2 (nu(1)) and N-H (nu(2)) stretch fundamentals. The complexation-induced frequency redshifts (Delta nu(1)approximate to 64, Delta nu(2)=183 cm(-1)) and the rotational structure of the nu(1) band are consistent with a T-shaped proton-bound CH3CNH+-H-2 geometry with a vibrationally averaged intermolecular bond length of 1.9 Angstrom. Ab initio calculations at the MP2 level of theory predict a binding energy of 1100 cm(-1) for the T-shaped complex, an intermolecular separation of 1.77 Angstrom, and frequency shifts of Delta nu(1)=88 cm(-1) and Delta nu(2)=215 cm(-1), in agreement with the experimental data. Whereas the CH3 internal rotation is nearly free (barrier V-b< 0.1 cm(-1)), H-2 rotation via a transition state with a linear -H ... H-H bond is severely hindered (V(b)approximate to 1050 cm(-1)). The lifetime of the nu(1) state (> 130 ps) greatly exceeds that of the lower lying nu(2) state (< 30 ps), indicating that the relaxation dynamics are mode-selective and not statistical.