The methodology of Cu(I)-mediated 1,3-dipolar cycloaddition was first applied in the synthesis of photoactive 1,2,3-triazolyl-modified vinylcarboranes of various architectures. As a result, a series of novel boron-enriched cluster compounds bearing a 1,2,3-triazol-vinyl-carborane conjugated system were synthesized in yields up to 92% and in mild reaction conditions. To reveal the “structure-luminescent properties” correlations attributed to the mutual influence of functional building blocks, the preliminary experiments on photophysical studies were carried out. The intramolecular charge transfer, as well as aggregation induced emission enhancement effects observed, could arouse a particular interest in these azaheterocyclic carboranes as challenging functional elements in the design of advanced materials for molecular electronics.