Herein are presented the 188.6 MHz C-13 NMR spectra (corresponding to 750 MHz H-1 resonance frequency) of a series of copolymers from ethylene and 1-octene monomers. These spectra permit the resolution of unique C-13 resonances from hexyl chain branches. The 750 MHz high-temperature pulsed field gradient (PFG), heteronuclear multiple quantum correlation (HMQC), and heteronuclear multiple-bond correlation (HMBC) two-dimensional (2D) NMR spectra of ethylene/1-octene copolymers are also presented. Data are presented from a new probe capable of performing high-temperature PFG coherence selection experiments at temperatures typical of those used in many polymer analyses. The performance of this probe is illustrated with PFG-HMQC and PFG-HMBC spectra of copolymers from ethylene/1-octene at 120 degreesC. Detailed unequivocal proof of the resonance assignments for poly(ethylene-co-1-octene) is reported. The 2D NMR spectra were used to confirm H-1 and C-13 chemical shift assignments previously determined by empirical methods. Quantitative analyses of the ethylene/1-octene copolymers were also performed.