Optimal conditions for separation and determination by HPLC or MEKC combined fungicides thiuram and tebuconazole are selected. The method of simultaneous determination of pesticides in grain offered. The recovery of pesticides was 90–95%. Lower bounds defined by the contents of pesticides, taking into account the concentration amounted to 0.005 mg kg−1 in the MEKC method, and 0.0025 mg kg−1 in the method of HPLC. The relative standard deviation of the results of the analysis is less than 0.09, analysis of the duration of 1–1.5 h.