The conformation and configuration analysis of the dimer bis(N,N-dimethyl-2,4-dimethylglutarylamide) was carried out by means of both conventional H-1 and C-13 NMR spectroscopy and advanced (INEPTLR and 2D HETCOR) methods. The gamma-gauche effect method appears to reproduce the observed chemical shift difference between m- and r-isomers. Stereochemical structure of poly(N,N-dimethylacrylamide) (PDMAA) was studied using proton spectrum (at the triad level) and DEFT spectra (at the triad and pentad level). For PDMAA prepared by radical polymerization, the Bernoullian statistics are required to fit the observed intensities at the pentad level.