Chemiluminescence (CL), as one class of luminescence driven by chemical reaction, exhibits obvious temperature-dependence in its light emission process. Herein, temperature-dependent CL emission of carbon nanodots (CDs) in the chemical reaction of peroxalate and hydrogen peroxide is demonstrated and temperature imaging based on the temperature-dependent CL has been established for the first time. In detail, the temperature-dependent CL emission of CDs in the chemical reaction of peroxalate and hydrogen peroxide is observed, and the linear relationship between the CL intensity and temperature is demonstrated in both the CL solution and film, enabling their applications in temperature sensing and imaging capabilities. The increase of the CL emission with temperature can be attributed to the accelerated electron exchange between the CDs and intermediate generated in the peroxalate system. Meter-scale chemiluminescent CD films have been constructed. The CL sensor based on the films presents a high spatial resolution of 0.4 mm and an outstanding sensitivity of 0.08 °C-1, which is amongst the best values for the thermographic luminophores. With the unique temperature response and flexible properties, non-planar, meter-scale and sensitive palm temperature imaging has been achieved. These findings present new opportunities for designing CL-based temperature probes and thermography.