Investigations into the optimization of the structural parameters of the macromolecular matrix with a view to designing efficient polymer supports for peptide synthesis are reported. The dependence on the chemical nature of the monomers, nature and extent of crosslinking the method of polymerization, hydrophobic-hydrophilic balance of the matrix, its chemical and mechanical stability, ease of functionalization, swelling!solvation behaviour, porosity and pore dimensions of the resin particles, and the chemical reactivity of the attached functional moiety on the variables of polymer synthesis are delineated. Acrylamide was crosslinked with highly hydrophilic tetraethyleneglycol diacrylate and triethyleneglycol dimethacrylate through medium polar N,N’-methylene-bis-acrylamide to highly hydrophobic and rigid divinylbenzene. These copoly(acrylamide)s were amino-functionalized by polymer-analogous reactions. The extent of functionalization, reactivity, porous nature, solvent compatibility and thermal behaviour of these resins was found to be dependent on the fine molecular character as well as on the nature and extent of crosslinking.