The microemulsion (water-in-oil) method is used to prepare novel silver catalysts onto three different carbon supports (multi-walled carbon nanotubes (MWCNT), mesoporous carbon (MC) and Vulcan carbon (C)). It allows to control the Ag particle growth and produces particles that range between 2 and 3 nm. The Ag-based catalysts are characterised by scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy (EDS). The electrocatalytic activity towards the oxygen reduction reaction (ORR) in 0.1 M KOH is studied using the rotating disc electrode method. High-angle annular dark-field (HAADF) STEM images reveal the Ag particle size range between 1.8 and 2.4 nm, and the EDS mapping shows uniform Ag distribution on the substrates used. Ag1/MC (two-step synthesis) and Ag2/MC (one-step synthesis) catalysts prepared onto the MC support show the highest mass activity of 30–37 A g−1. The two-step synthesis method is preferred to prepare Ag/MWCNT and Ag/C catalysts. The mass activity of the Ag1/MWCNT catalyst is more than two times higher than that of Ag2/MWCNT. Ag1/MWCNT shows the highest electrochemical stability after the accelerated durability test, with only a 6 mV shift in half-wave potential. The microemulsion method is very promising for the production of highly stable Ag-based catalysts with Ag particles smaller than 3 nm in size.