Eight polymerizable monoquaternary ammonium bromide cationic surfactants, and five non-polymerizable analogues have been prepared along with six structurally related polymerizable diquaternary ammonium dibromide cationic surfactants and five non-polymerizable analogues of these. The surface activity properties of all the surfactants have been characterized using surface tension and electrical conductivity measurements. The derived data (critical micelle concentrations, area per molecule at the air/water interface, etc.) have been compared and discussed in terms of the molecular structure of the surfactants and the valency of the salts. All of the surfactants have been employed (singly) as the emulsifier in small scale emulsion polymerizations of styrene and methylmethacrylate. In all cases well defined stable polymer latexes were obtained. The stability of these has also been further probed by the addition of various mono-, di- and trivalent electrolytes. Each emulsion has also been subjected to a freeze-thaw cycle. The stability results are discussed in terms of the molecular structure of the surfactants and, in particular, the efficiency of polymerizable vs non-polymerizable species have been compared and, likewise, the effectiveness of dicationic species vs monocationic ones.