A series of ethylene-vinyl alcohol copolymers (EVOH) with different comonomer contents were studied by both solution state and solid-state high-resolution 13C-NMR spectroscopy. A new assignment of 13C-CP/MAS spectrum of EVOH was given. It was demonstrated that the triple splitting of the signal of methine carbon of the vinyl alcohol unit in 13C-CP/MAS spectrum is caused by sequence distribution
tacticity and intra and inter molecular hydrogen-bonding interactions.