A systematic study of the aggregation behavior of alkyltriphenylphosphonium bromides (TPPB-n; n = 8, 10, 12, 14, 16, 18; here n is the number of carbon atoms in alkyl groups) in aqueous solutions has been carried out and compared with trimethyl ammonium bromides (TMAB-n). Critical micelle concentrations (cmcs) of TPPB-n and TMAB-n decrease with the number of carbon atoms with the slope parameter of ca.0.3. The low cmcs and effective solubilization power toward Orange OT indicate high micellization capacity of phosphonium surfactants. The low counterion binding parameter beta is revealed for TPPB-10 and TPPB-12, while high counterion binding of >= 80% is observed for high TPPB-n homologs. Values of the surface potential calculated on the basis of pK(a), shifts of p-nitrophenols is similar for both series and monotonously increase with alkyl chain length. Several points indicate non-monotonic changes within TPPB-n series. There are peculiarities of the tensiometry and solubilization plots for high homologs and above mentioned increases in counterion binding on transiting from low to high molecular weight surfactants. Differences in aggregation behavior between TPPB and TMAB series and between low and high homologs can be due to the specific structural character of the TPP+ cation, which is supported by X-ray data. (C) 2011 Elsevier Inc. All rights reserved.