Investigation concerning the structure and molecular dynamics of a nanocomposite made up of poly(p-phenylene sulfide) and silicon dioxide (SiO2) has been conducted by means of atomic force microscopy (AFM) and nuclear magnetic resonance (NMR). AFM and NMR studies of samples PPS in the neat and composite forms show that during annealing the fragmentation of big agglomerates of PPS take place. Between agglomerates and smaller aggregates there exist repulsion forces which are probably the source of fragmentation in the polymer network. The work has also proved that inside agglomerates and smaller aggregates of PPS dipolar magnetic interaction exist, whereas the electrostatic one occurs between them.