Calix[n]arenes, their hetero derivatives, are the most popular hosts for the supramolecular and materials chemistry as they can form stable inclusion complexes with charged or neutral molecules, including gases. This short review highlights the most prospective synthetic approaches for direct modification of calix[4]arene core with various functional moieties as well as selected patterns of direct C−H-modification of calix[6]arenes and calix[4]pyrroles.