Polyelectrolyte multilayers on silica colloids are investigated here using a combination of fast magic-angle spinning (MAS) and double-quantum (DQ) solid-state H-1 NMR techniques. 2D DQ H-1 NMR spectra of the bulk complex and the multilayer films (see Figure) are found to be similar, revealing complexation between the alternating layers of poly(sodium 4-styrenesulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC).