Exsolution of metal nanoparticles (NPs) on perovskite oxides has been demonstrated as a reliable strategy for producing catalyst‐support systems. Conventional exsolution requires high temperatures for long periods of time, limiting the selection of support materials. Plasma direct exsolution is reported at room temperature and atmospheric pressure of Ni NPs from a model A‐site deficient perovskite oxide (La0.43Ca0.37Ni0.06Ti0.94O2.955). Plasma exsolution is carried out within minutes (up to 15 min) using a dielectric barrier discharge configuration both with He‐only gas as well as with He/H2 gas mixtures, yielding small NPs (<30 nm diameter). To prove the practical utility of exsolved NPs, various experiments aimed at assessing their catalytic performance for methanation from synthesis gas, CO, and CH4 oxidation are carried out. Low‐temperature and atmospheric pressure plasma exsolution are successfully demonstrated and suggest that this approach could contribute to the practical deployment of exsolution‐based stable catalyst systems.