A key hypothesis in the field of exoplanet atmospheres is the trend of atmospheric thermal structure with planetary equilibrium temperature. We explore this trend and report here the first statistical detection of a transition in the near-infrared atmospheric emission between hot and ultra-hot Jupiters. We measure this transition using secondary eclipse observations and interpret this phenomenon as changes in atmospheric properties, and more specifically in terms of transition from non-inverted to inverted thermal profiles. We examine a sample of 78 hot Jupiters with secondary eclipse measurements at 3.6 and 4.5 μm measured with Spitzer Infrared Array Camera. We calculate the planetary brightness temperatures using PHOENIX models to correct for the stellar flux. We measure the deviation of the data from the blackbody, which we define as the difference between the observed 4.5 μm eclipse depth and that expected at this wavelength based on the brightness temperature measured at 3.6 μm. We study how the deviation between 3.6 and 4.5 μm changes with theoretical predictions with equilibrium temperature and incoming stellar irradiation. We reveal a clear transition in the observed emission spectra of the hot Jupiter population at 1660 ± 100 K in the zero albedo, full redistribution equilibrium temperature. We find the hotter exoplanets have even hotter daysides at 4.5 μm compared to 3.6 μm, which manifests as an exponential increase in the emitted power of the planets with stellar insolation. We propose that the measured transition is a result of seeing carbon monoxide in emission due to the formation of temperature inversions in the atmospheres of the hottest planets. These thermal inversions could be caused by the presence of atomic and molecular species with high opacities in the optical and/or the lack of cooling species. Our findings are in remarkable agreement with a new grid of 1D radiative and convective models varying metallicity, carbon to oxygen ratio (C/O), surface gravity, and stellar effective temperature. We find that the population of hot Jupiters statistically disfavors high C/O planets (C/O ≥ 0.85).