Despite the popular use of citrate for the reduction of silver ions, this process suffers from slow crystal growth and broad size distribution. The rapid and effective synthesis of highly concentrated and stable spherical silver nanoparticles (AgNPs) confined in the surfactant-rich phase of thermoresponsive 3-(alkyldimethylammonio)-propyl sulfate surfactants obtained after reaction with citrate ions at high temperature is described. The present approach using the zwitterionic surfactant offers an alternative rapid approach for production of AgNPs and an in situ phase separation step that serves to "extract" and concentrate the AgNPs in the surfactant-rich phase. Almost all (synthetic yield 99.9%, extraction efficiency 98.6%) of the synthesized AgNPs with a diameter of 21.0 ± 2.5 nm were incorporated into the phase-separated surfactant-rich phase at pH 11, and the capacity (maximum concentration) was 3.4 × 1013 particles/mL. The AgNPs were stable upon long-term storage (at least 3 months).