A review of cycloaddition reactions of 3,6-disubstituted-1,2,4,5-tetrazines developed to regiospecifically couple together alicyclic reagents, with the particular emphasis on norbornenes. A variety of large polycyclic rigid molecules containing one or more functional groups precisely positioned both in distance and relative orientation onto an inert carbocyclic frame could be effectively produced by s-tetrazine coupling protocol.