Generation-4 poly(amidoamine) dendrimers (G4-PAMAM) were cross-linked using gluteraldehyde to obtain aldehyde activated G4-PAMAM and cross-linked G4-PAMAM termed pre-megamers, which were grafted with octadecylamine (ODA) in chloroform (CHCl3). Statistical megamer morphologies and particles were prepared by an emulsification solvent evaporation method using an ODA-premegamer/CHCl3 solution, surfactant and water. Physico-chemical characterization of the premegamers and megamers by various spectroscopic and microscopic techniques demonstrated their formation and properties useful in diagnostic and chromatographic applications.