AbstractElectron diffraction data from a series of paraffins epitaxially crystallized on benzoic acid are used to determine their crystal structures. Even‐chain paraffins fromn‐C32H66ton‐C60H122are shown to crystallize isostructurally as the orthorhombic polymorph described forn‐C36H74. Like the even‐chain compounds, odd‐chain paraffins do not crystallize in their lowest‐energy form. A quantitative zonal crystal structure analysis forn‐C33H74suggests that the molecular packing is in the B‐polymorphic form proposed earlier