In this paper, we study compact samples of pyrophoric nickel powders with the average particle size of 85 nm, obtained by the chemical-metallurgical method. For the first time, it is experimentally shown that it is possible to passivate compact samples with a diameter of 3 mm from pyrophoric nickel powders with nanosized particles in air. For a relative density of 0.4 to 0.5, the passivation time is only 3–5 s. According to the X-ray phase analysis data, only the Ni phase is observed in passivated samples. It is found that passivated samples retain their thermal stability in air upon slow (<10 deg/s) heating to ~200°C, which is an important parameter for fire safety when handling nanopowders. The electron microscopic analysis of the passivated samples did not reveal traces of sintering of nickel nanoparticles, including after checking for thermal stability. The uniform distribution of oxygen over the passivated samples according to the data of energy dispersive analysis (the standard deviation is 0.9 at %) indicates the volumetric nature of the interaction of the samples with air during passivation. For the obtained passivated samples, the critical heating conditions were determined, under which self-ignition occurs, which is in agreement with N.N. Semyonov’s classical theory of thermal explosion.