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 (O_V) 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 (O_V) and impurity energy levels, effectively reducing the band gap and improving emissivity in the wavelengths below 6 μm. In particular, the infrared emissivity of (Pr_0.3Y_0.3Ca_0.4)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.