FengYun-3 (FY-3) Visible Infrared Radiometer (VIRR), along with its predecessor, Multispectral Visible Infrared Scanning Radiometer (MVISR), onboard FY-1C&D have had continuous global observation more than 14 years. This data record is valuable for weather prediction, climate monitoring, and environment research. Data quality is vital for satellite data assimilations in Numerical Weather Prediction (NWP) and quantitative remote sensing applications. In this paper, the accuracies of radiometric calibration for VIRR onboard FY-3A and FY-3B, in thermal infrared (TIR) channels, are evaluated using the Low Earth Orbit (LEO)-LEO simultaneous nadir overpass intercalibration method. Hyperspectral and high-quality observations from Infrared Atmosphere Sounding Instrument (IASI) onboard METOP-A are used as reference. The biases of VIRR measurements with respect to IASI over one-and-a-half years indicate that the TIR calibration accuracy of FY-3B VIRR is better than that of FY-3A VIRR. The brightness temperature (BT) measured by FY-3A/VIRR is cooler than that measured by IASI with monthly mean biases ranging from −2 K to −1 K for channel 4 and −1 K to 0.2 K for channel 5. Measurements from FY-3B/VIRR are more consistent with that from IASI, and the annual mean biases are 0.84 ± 0.16 K and −0.66 ± 0.18 K for channels 4 and 5, respectively. The BT biases of FY-3A/VIRR show scene temperature-dependence and seasonal variation, which are not found from FY-3B/VIRR BT biases. The temperature-dependent biases are shown to be attributed to the nonlinearity of detectors. New nonlinear correction coefficients of FY-3A/VIRR TIR channels are reevaluated using various collocation samples. Verification results indicate that the use of the new nonlinear correction can greatly correct the scene temperature-dependent and systematic biases.