The results of an1H and13C nmr study of the threesyn-pyridine aldoximes are reported. Observed6J(Hα,Hpara) values in the 2- and 3-pyridine aldoximes indicate that the oxime group is twisted approximately 20° out of the pyridine ring plane. Stereospecific5J(Hα,Hmeta) values measured for acetone solutions of 2-pyridine aldoxime indicate that the ratio of the NCCNtransconformation to the NCCNcisconformation is 0.86 ± 0.14. The results of similar measurements on 3-pyridine aldoxime give 0.60 ± 0.10 for the ratio of the C2CCNtransand C2CCNcisconformations.Abinitiomolecular orbital calculations are in good qualitative agreement with experiment. Carbon-13 chemical shifts of the oximes are compared with those previously measured for the parent aldehydes.