In view of selectively recovering precious contents in electronic waste by combined electrochemical leaching and deposition step in the same cell, this study presents electrochemical investigations of the two reactions conducted in green deep eutectic solvents (DESs) for the case of silver. In addition to ethaline 1 : 2 formed from choline chloride and ethylene glycol, propeline 1 : 3 with less nocive propylene glycol was tested. Determination of the density, viscosity and conductivity of the two DES depending on temperature and their water content could lead to ionicity values from 0.70 to 0.90, with a negative effect of these operating parameters. Pure silver can be leached at 1 mA cm⁻² with faradaic yield near 100% from the two DES, provided sufficient temperature and water content below 5 wt%. Electrodeposition was thoroughly examined by cyclic voltammetry and amperometry at transient or steady state at a rotating electrode, leading to Ag(I) diffusivity values in the two DES. Kinetic parameters of the electrodeposition reaction, modelled as irreversible, were also estimated from cyclic voltammograms. Thick silver deposits were produced in 24 h-long tests at 60 °C and 0.25 mA cm⁻² in a dry atmosphere with nearly 100% current efficiency. The deposits were formed by little coalesced regular grains of size 15–20 μm and exhibiting fair adherence.