jats:titleAbstract</jats:title>jats:pVolcanism is a major and long‐term source of volatile elements such as C and H to Earth's atmosphere, likely has been to Venus's atmosphere, and may be for exoplanets. Models simulating volcanic growth of atmospheres often make one of two assumptions: either that atmospheric speciation is set by the high‐temperature equilibrium of volcanism or that volcanic gases thermochemically reequilibrate to the new, lower, temperature of the surface environment. In the latter case, it has been suggested that volcanic atmospheres may create biosignature false positives. Here, we test the assumptions underlying such inferences by performing chemical kinetic calculations to estimate the relaxation timescale of volcanically derived atmospheres to thermochemical equilibrium, in a simple 0D atmosphere neglecting photochemistry and reaction catalysis. We demonstrate that for planets with volcanic atmospheres, thermochemical equilibrium over geological timescales can only be assumed if the atmospheric temperature is above ∼700 K. Slow chemical kinetics at lower temperatures inhibit the relaxation of redox‐sensitive species to low‐temperature thermochemical equilibrium, precluding the production of two independent biosignatures through thermochemistry alone: 1. ammonia and 2. the cooccurrence of COjats:sub2</jats:sub> and CHjats:sub4</jats:sub> in an atmosphere in the absence of CO. This supports the use of both biosignatures for detecting life. Quenched at the high temperature of their degassing, volcanic gases also have speciations characteristic of those produced from a more oxidized mantle, if interpreted as being at thermochemical equilibrium. This therefore complicates linking atmospheres to the interiors of rocky exoplanets, even when their atmospheres are purely volcanic in origin.</jats:p>