The formation of amphiphilic complexes of poly(allylammonium chloride) carrying pendant maltose residue (PAAHCl-Mal) with sodium alkylsulfonates (sodium octanesulfonate (NaOcS), sodium dodecanesulfonate (NaDoS), sodium hexadecanesulfonate (NaHeDeS)) in aqueous solution was studied by means of turbidimetry, fluorescence spectroscopy using pyrene, H-1 NMR and viscometry. In contrast to the complex of PAAHCl homopolymer with NaDoS, which precipitated at the ratio of the concentration of DoS to the concentration of ammonium group in the polymer, [DoS]/[NH3+] = 0.01, the complexes of PAAHCl-Mal(14) containing 14 mol% maltose residue with NaDoS are water-soluble over the whole range of compositions of the mixture, including the electroneutralized condition, [DoS]/[NH3+] = 1. In the mixture of PAAHCl-Mal(14) and NaDoS at [DoS]/[NH3+] = 1, the ratio (I3H1) of the intensities of third and first vibrational bands of pyrene was 0.83, indicating that the complexation of PAAHCl-Mal(14) with NaDoS gives rise to a hydrophobic domain. In addition to these results, from 1H NMR and viscosity measurements of the PAAHCl-Mal(14) and NaDoS system, it seems that these species form a micelle like aggregate with a hydrophobic core from the surfactants bound to the polymer and a hydrophilic outer shell from the maltose residues. Moreover, the effects of content of maltose residue in the polymer and alkyl chain length of surfactant on the complexation of PAAHCl-Mal with alkylsulfonates are discussed.