This study describes the molecular dynamics (MD) simulations of the 4‐n‐alkyl‐4′‐cyanobiphenyl (nCB, n=5–9) liquid crystal homologous series at a selected temperature in the nematic phase. The order parameters and the biaxialities for five mesogens were found to be reasonable agreement with experiments. The orientational distributions of C–C bonds in alkyl chain of nCB were calculated and given for 6CB and 7CB. The odd‐even effect was also discussed.