Aflatoxins B1, B2, G1, G2 (AFB1, AFB2, AFG1, AFG2), ochratoxin A (OTA), and zearalenone (ZEA) in dried and ground red pepper (Capsicum annuum) were simultaneously analyzed with high-performance liquid chromatography coupled to fluorescence detection after post-column derivatization. The analytical method was validated for specificity, selectivity, linearity, limits of detection and quantification, recovery, precision, and measurement of uncertainty. The limits of detection and quantification were 0.10 and 0.25 μg/kg for AFB1, 0.04 and 0.06 μg/kg for AFB2, 0.14 and 0.50 μg/kg for AFG1, 0.05 and 0.10 μg/kg for AFG2, 0.12 and 0.45 μg/kg for OTA, and 4.00 and 13.25 μg/kg for ZEA, respectively. The average recoveries ranged from 80.4 to 98.5% for different concentrations of AFB1, AFB2, AFG1, AFG2, OTA, and ZEA in spiked samples. The measurement uncertainties were 0.64 to 1.62 μg/kg for AFB1, 0.24 to 0.45 μg/kg for AFB2, 0.79 to 2.19 μg/kg for AFG1, 0.32 to 0.61 μg/kg for AFG2, 0.81 to 2.31 μg/kg for OTA, and 8.48 to 26.25 μg/kg for ZEA. This method was successfully applied for the simultaneous determination of mycotoxins for 78 red peppers collected from Korean and Indian markets. Aflatoxins (sum of AFB1, AFB2, AFG1, and AFG2) were detected in 2% of nonpacked samples (n = 23) and 43% of packed samples (n = 55), at levels of 0.04 to 38.03 μg/kg. OTA was detected in 4% of nonpacked samples and 48% of packed samples, at levels of 0.15 to 56.30 μg/kg. ZEA was not detected in any samples. These findings indicate that the analytical method described here is suitable for the routine determination of the amounts of AFs, OTA, and ZEA in dried and ground red pepper.