The development of broadband, high-performance infrared radiation materials is crucial for energy conservation and applications in aerospace and industrial sectors. Rare earth orthochromites, such as PrCrO3, exhibit good thermal stability and high infrared emissivity beyond the 6 μm wavelength range. However, their large bandgap limits their infrared emissivity before 6 μm, significantly impacting their potential applications. Herein, we have successfully enhanced the thermal emissivity of PrCrO3 by manipulating oxygen vacancies (OV) and accompanying impurity levels, leading to the synthesis of five rare earth orthochromites. Compared with pristine PrCrO3, co-doping of Ca, Co, and Mn introduced oxygen vacancies (OV) and impurity energy levels, effectively reducing the band gap and improving emissivity in the wavelengths below 6 μm. In particular, the infrared emissivity of (Pr0.3Y0.3Ca0.4)CrO3 in the wavelengths of 0.78–2.5 μm reaches 0.89, which is double than that of pristine PrCrO3. Furthermore, its thermal stability is excellent, as demonstrated by thermal shock experiments at 1500 ℃ for five cycles. More importantly, the developed orthochromites can be applied as a coating on substrates such as alumina ceramic sheets, exhibiting an average infrared emissivity of 0.95 and remarkable radiative heat transfer capability. This research contributes to the advancement of high-performance infrared radiation materials by vacancy engineering.