Recent optical spectra of post-AGB stars show the presence of C2, CN, and CH+ originating in the circumstellar shell. We present here new, higher resolution spectra which provide constraints on the physical parameters and information on the line profiles. An empirical curve of growth for the C2 Phillips and CN Red system lines in the spectrum of HD 56126 yields b = 0.050+0.59 −0.23 km s−1. CH+ (0,0) emission lines in the spectrum of the Red Rectangle have been resolved with a FWHM ≈ 8.5± 0.8 km s−1. The circumstellar CN lines of IRAS 08005-2356 are resolved into two separate components with a velocity separation of Δv = 5.7 ± 2.0 km s−1. The line profiles of CN of HD 235858 have not been resolved.