Results are reported, providing the basis for an elegant new process for metal recovery from acidic solutions, by integrating solvent extraction (SX) and electrowinning (EW) in a single process, rather than operating them separately, as in conventional SX-EW processes. Calixarene-tetramide and its thio-analogue were used for the extraction of silver(I) ions from aqueous phases into dichloromethane, both compounds achieving extraction efficiencies > 90%. The effects were determined of extractant and silver(I) concentrations, aqueous phase pH, and the presence of sodium ions, on the distribution of Ag(I) between aqueous and organic phases. Due to the impossibility of stripping the extracted metal conventionally, electro-reductive stripping of silver(I) from the loaded organic phase was carried out in the calixarene/nitric acid two-phase system. The effects were also investigated of current density or electrode potential on silver deposition current efficiencies and cell voltages. Based on experimental data, a new process for silver(I) removal from very dilute solutions was proposed that showed high percentage extractions of silver(I) from the aqueous phase, coupled to direct EW of silver from the calixarene complex in the loaded organic phase, regenerating the extractant for recycle. Current efficiencies in the range from 60% to 90% and cell voltages < 3.5 V were achieved simultaneously in this process.