Acrylamide hydrogels were synthesized in a series of hydro-organic solvents to examine how solvent affects the network structure by influencing properties of the first formed polymer in the reaction mixture. The looser and more heterogeneous network structure of gels formed in aqueous solutions of ethylene glycol or propylene glycol was found to be largely due to the reduced chain lengths of the primary polymer molecules. Results from NMR analysis of the monomer, and intrinsic viscosity measurements of the polymer in various solvents indicate that solvent effects on the reactivity of the monomer and the propagating radical impose an overriding control over properties of the resultant networks. (C) 2003 Elsevier Ltd. All rights reserved.