1H and13C NMR chemical shift assignments were obtained for the local anesthetics etidocaine (1) and etidocaine hydrochloride (2) in CDCl3solution, as well as for2in D2O solution. The COSY experiment was employed for proton-proton correlation, while onebond and long-range 2D heteronuclear techniques allowed the assignments of all13C chemical shifts in each molecule. Etidocaine has a chiral carbon; etidocaine hydrochloride has, in addition to the natural chiral center, an acid-induced chirality at the protonated amine nitrogen, resulting in solvent-dependent diastereomers. Ten of the fourteen magnetically nonequivalent13C nuclei of2exhibit doubled13C resonance peaks (50.3 MHz, 20°C, CDCl3solution) due to the presence of the two diastereomers.