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The quality of grass samples used for animal feed by combining mycotoxin measures and mycological determination of mycobiota were explored. The samples of the plant material were collected in 2014 in two stages: before the first mowing (May–June) and before the second one (July–August) from the fields of stock-farms located in northwestern part of the Russia. All samples were divided into three types: grasses, mixture of different grasses and clover, alfalfa mixed with timothy. The occurrence of aflatoxin B1, alternariol, citrinin, cyclopiazonic acid, deoxynivalenol, diacetoxyscirpenol, emodin, ergot alkaloids, fumonisins, mycophenolic acid, ochratoxin A, PR-toxin, roridin A, sterigmatocystin, T-2 toxin, and zearalenone were determined using ELISA. The multiple fungal and mycotoxin contaminations are already formed in plant tissues by the moment of first mowing. The complexes of mycotoxins including up to 14–16 components and the combined character of plant contamination quite correspond to the taxonomic variety of mycobiota.