7-Cyanoexahelicenehas been prepared in racemic form through a short photochemical synthetic approach and its enantiomeric separation was studied and allowed to obtain (P)- and (M)-enantiomers in 100% ee and > 98.5% ee, respectively. The optical rotatory dispersion and electronic circular dichroism (ECD) spectra of the resolved ones were measured. Other optical properties such as UV and photoluminescence as well as the electrochemical behavior were also examined in solutions.