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The presented paper is devoted to an innovative way of teaching mathematics, specifically the subject combinatorics in high schools. This is because combinatorics is closely connected with the beginnings of informatics and several other scientific disciplines such as graph theory and complexity theory. It is important in solving many practical tasks that require the compilation of an object with certain properties, proves the existence or non-existence of some properties, or specifies the number of objects of certain properties. This paper examines the basic combinatorial structures and presents their use and learning using relations through the Placemat method in teaching process. The effectiveness of the presented innovative way of teaching combinatorics was also verified experimentally at a selected high school in the Slovak Republic. Our experiment has confirmed that teaching combinatorics through relationships among talented children in mathematics is more effective than teaching by a standard algorithmic approach. [ABSTRACT FROM AUTHOR]