Conductance behaviors of reverse micelles/microemulsions have been investigated by means of electrical conductometry, with em-phasis on the influences of water content, bis(2-ethylhexyl) phos-phoric acid (HDEHP) content, and temperature. Two systems were prepared and studied, i.e., sodium bis(2-ethylhexyl) sulfosuccinate (AOT) in n-heptane (H(2)O/AOT/n-heptane) and sodium bis(2-ethylhexyl) phosphate (NaDEHP) in n-heptane (H(2)O/NaDEHP/ n-heptane). The conductance behaviors of AOT+HDEHP and NaDEHP+HDEHP systems are dependent upon water content (W(0), expressed as the molar ratio of solubilized water and surfactant(s)), HDEHP content, and temperature. With an increase of water content, the conductivity-W(0) curves of the AOT+HDEHP system show maximum conductivity and no percolation conductance, different from that of the AOT system. The conductivity of the NaDEHP+HDEHP system varies with the NaDEHP to HDEHP ratio. For the systems with the NaDEHP to HDEHP ratios of 80 : 20 and 70 : 30, both maximum conductivity and percolation phenomenon can be observed, while for the system with the NaDEHP to HDEHP ratio of 90 : 10, neither maximum conductance nor percolation conductance occurs. With varying temperature, markedly different conductance behaviors were observed in AOT+HDEHP and NaDEHP+HDEHP systems. Percolation conductance occurs in the AOT+HDEHP system and the onset temperature for percolation conductance decreases with increasing water content and/or HDEHP content. In the H(2)O/(NaDEHP, HDEHP)/n-heptane system, however, the conductivity decreases markedly with increasing temperature until a minimum, followed by a slow recovery of the conductivity. These phenomena could be attributed to the different aggregation states of the surfactants and the different transition mechanisms of charge carriers in respective systems at different water contents, HDEHP contents, and temperatures. Copyright 2001 Academic Press.