Silver nanoparticles (NPs) were synthesized in organic solvents. Spontaneous reduction of silver salts takes place in N,N′-dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) at room temperature. The formed colloids are not stable without a stabilizing agent, hence rarely used, and inexpensive organic molecules (β-cyclodextrin and cholic acid) were used as surface modifiers in DMF. The stabilization was successful; the Ag NPs remained stable for more than 3 months. Additionally, Ag NPs were prepared using Ag-2-ethylhexanoate and Na-citrate as capping agent in DMSO. The resulting NPs are stable, of 4.4 nm average size, and at the same time reactive for catalytic purposes. The interaction of Ag NPs with pollutant atmospheric gases (NO and SO2) was studied. UV–visible spectra show the oxidation of silver and the very efficient reduction of NO at room temperature. SO2 molecules are adsorbed on the NPs surface, causing their aggregation and precipitation.