The phase behaviors, interfacial composition, thermodynamic properties and structural characteristics of water-in-oil microemulsions under varied molar ratio of water to surfactant (omega) at 303 K and also by varying temperatures at a fixed omega (= 40) by mixing with 1-pentanol and decane or dodecane in absence and presence of sodium chloride have been Studied by the method of dilution. The surfactants used were cetyl pyridinium chloride (CPC), sodium dodecyl sulfate (SDS) and polyoxyethylene (23) lauryl ether (Brij-35). The compositions of 1-pentanol and the surfactant at the interfacial region, the distribution of 1-pentanol between the interfacial region and the continuous oil phase, and the effective packing parameter (P-eff) at the threshold level of stability have been estimated. The thermodynamics of transfer of 1-pentanol from the continuous oil phase to the interface have been evaluated. The structural parameters viz. radii of the droplet (R-e) and the waterpool (R-w), effective thickness of the interfacial layer (d(1)), average aggregation numbers of surfactants ((N) over bar (s)) and the cosurfactant (1-pentanol) ((N) over bar (a)) and the number of droplets (N-d) have also been estimated. The prospect of using these w/o microemulsions for the synthesis of nanoparticles with small size, have been discussed in the light of the radii of the droplet, and waterpool, the extent of variation of effective thickness of the droplet under varied molar ratio of water to surfactant and temperature. An attempt has been made to rationalize the results in a comprehensive manner. (C) 2007 Elsevier Inc. All rights reserved.