AbstractCyclam is a well‐known example of a polyaza macrocycle. However, there are few reports of its optically active versions. In this study, we synthesized highly symmetric optically active cyclam (S,S,S,S)‐5,7,12,14‐tetraphenyl‐1,4,8,11‐tetraazacyclotetradecane, which has four phenyl groups on the cyclam skeleton, and derivatized it in various ways. We were able to synthesize a chiral Cu complex, an N‐ethyl derivative, and a dithiourea from this optically active cyclam. The structures of the chiral Cu complex and dithiourea were verified by single‐crystal X‐ray diffraction analysis.