A series of surfactants were designed and synthesized or use as clay modification reagents to investigate the impact of theft chemical structure on the nanocomposites morphology obtained following polymerization. The behavior of the surfactant-modified clays at three different stages were investigated: after ion exchange, following dispersion in styrene monomer, and once polymerization was complete, The propensity of the styrene monomer to swell the surfactant-modified clay was observed to be a useful indicator of compatibility and predictor of the resultant polystyrene nanocomposite morphology which was directly observed using small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (TEM). It was found that the key components of surfactant design driving exfoliated morphologies were (1) the position of the ammonium group, (2) the inclusion of a polymerizable group, (3) the solubility of the surfactant in the monomer, (4) the length of the alkyl chain, and (5) sufficient concentration of surfactant used to exchange the clay. This understanding should lead to better design of clay modifications for use in polymer nanocomposites.