Up to now, information about biogeochemistry of many trace elements is scarce. Meanwhile, all the elements are always present in soil and plants. It may be suggested that the trace elements also play certain role in the biogeochemical processes. The aim of the research was to study bioaccumulation of poorly investigated trace elements (scandium, cerium, europium, hafnium, and tantalum) and well-known elements (chromium, iron, cobalt, zinc, and arsenic) in two crops, oats and barley, and examine how these elements interact with each other as they absorbed by plants. The plants were grown in the soils that differed in their parameters and in level of contamination. Although oats and barley are botanically similar and were grown under the same conditions, the plants differed in the ability to accumulate many elements. The uptake of the elements by the plants also depended on type of soil. For example, concentrations of Cr, Fe, Co, As, Sc, Ce, Eu, Hf, and Ta in roots of the oats grown in slightly contaminated soil were much higher as compared to the concentrations of the elements in roots of the barley grown in the same soil. In leaves of the oats grown in moderately contaminated soil, the concentrations of Cr, As, Ce, Eu, and Ta were statistically significantly higher than those in leaves of the barley grown in the soil. In soils and in plants, relationships between elements were both similar and different. A statistically significant correlation was found between the poorly investigated trace elements and well-studied elements.