A comprehensive study of micellization and microemulsion formation of a cationic gemini surfactant (tetramethylene-1,4-bis(dimethyltetradecylammonium bromide; 14-4-14) in the absence or presence of hydrophobically modified polyelectrolyte, sodium carboxymethylcellulose (NaCMC), has been conducted by conductometry, tensiometry, microcalorimetry, and fluorimetry methods at different temperatures. Both critical micelle concentration and degree of ionization of the surfactant have been observed to increase with increasing temperature. The interfacial and thermodynamic parameters were evaluated. The standard Gibbs free energy of micellization (Delta G(m)degrees) is negative, which decreases with increase in temperature. Larger entropic contribution is observed compared to the enthalpy. The interaction of 14-4-14 with NaCMC produces coacervates which was determined from turbidimetry method. The pseudoternary phase behavior of the microemulsion systems comprising water (or NaCMC as additive), 14-4-14, isopropanol (IP) or n-butanol (Bu) as cosurfactant, and isopropyl myristate (IPM) were studied at 298 K. Phase diagrams reveal that IP derived microemulsions (in the absence of NaCMC) offer a large isotropic region compared to Bu-derived systems at comparable physicochemical conditions. Increasing the concentration of IP or Bu decreases the isotropic region in the phase diagram. NaCMC influences the microemulsion zone, depending upon its concentration, and type of cosurfactant and surfantant/cosurfactant ratio. Dynamic light scattering and conductometric measurements show the size of the droplet, threshold temperature of percolation, scaling parameters, and activation energy of the percolation process of 14-4-14/IP or Bu derived microemulsion systems without/with NaCMC at various physicochemical conditions. Bu exerts a greater effect to reduce ?t than IP as a cosurfactant (in the absence of NaCMC) at comparable. On the other hand, IP showed better percolating effect than Bu in the presence of NaCMC. Bu and IP (as cosurfactant) and NaCMC (as additive) influenced the microemulsion droplet size (D-h) to different extents under comparable conditions. Temperature insensitive microemulsions have been reported at the studied temperature range (298353 K). 14-4-14/IP (1:2)-derived microemulsion showed a fractured surface at fixed omega = 15, where ? is the water and surfactant molar ratio, and temperature (298 K); whereas, large scale mesospheres comprising multiple closely winded nanoslices and spheroid morphology were formed in 14-4-14/IP and 14-4-14/Bu microemulsions, respectively, in the presence of 0.01 g % NaCMC, at comparable conditions. These systems revealed good antimicrobial activity toward the strains of Gram-positive Bacillus subtilis and Gram-negative Escherichia coli bacteria at 298 K, and inhibitory effect was governed by omega, type of cosurfactant, and bacterial strains.