Solutions of liposomes composed of binary mixtures of anionic dioleoylphosphatidylserine (DOPS) and zwitterionic dioleoylphosphatidylcholine (DOPC) are investigated with label-free angle-resolved (AR) second harmonic scattering (SHS) and electrophoretic mobility measurements. The membrane surface potential is extracted from the AR-SHS response. The surface potential changes from −10 to −145 mV with varying DOPS content ( from 0% to 100%) and levels off already at ∼ 10 % DOPS content. The ζ-potential shows the same trend but with a drastically lower saturation value (−44 mV). This difference is explained by the formation of a condensed layer of Na+ counterions around the outer leaflet of the liposome as predicted by charge condensation theories for polyelectrolyte systems.