A broad-line H-1-NMR study was carried out; to examine the local structure of poly(methylmethacrylate) (PMMA) grafted onto Poly(tetrafluoroethylene) (PTFE). The NMR spectra were observed for three different samples with 1.0, 5.4, and 7.0 wt % PMMA over the temperature range from 150 to 380 K. With the help of selectively deuterated PMMA (PMMA-d(5) and PMMA-d(8))-grafted samples, the NMR spectra were analyzed in terms of two components-a Gaussian (G) component, and a Lorentzian (L) component. Based on the second moments ([Delta H-2]) analysis, the L and G components were attributed to the H-1-H-1 dipolar interactions within one CH3 group and the interactions of CH, groups that are closely located in aggregated PMMA chains. Combining the results with the temperature dependence of [Delta H-2] and the angular resolved XPS, the location and rotational motion of PMMA grafted onto PTFE are discussed.