The interactional and morphology behavior of mixed system embracing chlorpromazine hydrochloride (CPZ) drug and surface active biamphiphilic ionic liquids (BAILs); 1-hexyl-3-methylimidazolium dodecylsulfate ([C₆mim][C₁₂OSO₃]) and 1-butyl-3-methylimidazolium octylsulfate ([C4mim][C₈OSO₃]) at pH 7 have been investigated to develop new strategies to use BAILs as carriers of pharmaceutical active compounds. UV-vis absorption spectroscopy and cyclic voltammetry (CV) methods are used to shed light on the foremost interactions governing CPZ + BAILs mixtures. The higher value of binding constant (K_a) and Gibbs free energy change (DG) for CPZ + [C₆mim][C₁₂OSO₃] mixture, determined from absorbance measurements depict the existence of more attractive interactions than CPZ + [C₄mim] [C₈OSO₃]. The composition mediated self-assembly of CPZ + BAIL mixed aggregates in bulk has been investigated by small angle neutron scattering (SANS), dynamic light scattering (DLS) and zeta potential measurements.