A study was carried out on the influence of different aza crown ethers on the electric percolation of AOT/isooctane/water microemulsions. A dual behavior of the aza crown ethers with regard to the percolative phenomenon was observed: low additive concentration causes an increase in the percolation temperature, whereas at high additive concentration a reduction in the percolation temperature of the system was observed. This dual behavior allowed us to define the compensation concentration, which corresponds the aza crown ether concentration at which there is no effect on the percolative phenomenon. We observed a correlation between the effect exerted by the aza crown ethers and the size of the cavity. This shows the importance of the capacity to complexate Na+ and solubilize it in the interface and the continuous medium on the electric percolation. We also observed a correlation between the effect of the aza crown ethers on the percolation temperature and their external size. This shows the importance of their inclusion in the interface on the percolative phenomenon. Such an inclusion modifies the properties of the AOT film, facilitating the exchange of matter between droplets. A satisfactory multiparametric correlation between the compensation concentration, the distribution of the aza crown ether between water and 1-octanol, and the number of electron-donor atoms (O and N) in the crown ether was obtained. The effects have been compared with those corresponding to the crown ethers. (c) 2006 Elsevier Inc. All rights reserved.