This article aims to evaluate deoxynivalenol occurrence in triticale crops in Romania in years with extreme weather events (2012: Siberian anticyclone with cold waves and heavy snowfall; 2013 and 2014: “Vb” cyclones with heavy precipitation and floods in spring). The deoxynivalenol level in triticale samples (N = 236) was quantified by ELISA. In Romania, the extreme weather events favoured deoxynivalenol occurrence in triticale in Transylvania and the Southern Hilly Area (44–47° N, 22–25° E) with a humid/balanced-humid temperate continental climate, luvisols and high/very high risk of floods. Maximum deoxynivalenol contamination was lower in the other regions, although heavy precipitation in May–July 2014 was higher, with chernozems having higher aridity. Multivariate analysis of the factors influencing deoxynivalenol occurrence in triticale showed at least a significant correlation for all components of variation source (agricultural year, agricultural region, average of deoxynivalenol, average air temperature, cumulative precipitation, soil moisture reserve, aridity indices) (p-value < 0.05). The spatial and geographic distribution of deoxynivalenol in cereals in the countries affected by the 2012–2014 extreme weather events revealed a higher contamination in Central Europe compared to southeastern and eastern Europe. Deoxynivalenol occurrence in cereals was favoured by local and regional agroclimatic factors and was amplified by extreme weather events.