Luminescence spectra of oxygen rich propane gas flames have been recorded in medium-high resolution. Well separated vibrational bands for electronic transitions in C₂, CH and OH are observed. The spectra are found to be rich, both in terms of vibrational and rotational structure. A large number of bandheads with varying intensities are observed in C₂(d(³P_g)->a(³P_u)). Bands are found to be degraded toward the blue (C₂(d(³P_g)->a(³P_u)), red (CH(B(²S^-)-> X(²P)) and OH(A(²S⁺)->X(²P)))  or to be nearly symmetric in shape (CH(A(²D)->X(²P))). Clear rotational structure with identifiable rotational line series (P,Q and R) are observed for  CH(A->X and B->X). The relative intensities of vibrational bands vary considerably from one system to another. These observations can be used to demonstrate a number of basic principles in quantum chemistry and spectroscopy,  relevant to electronic, vibrational and rotational structure of molecules as well as transition probabilities. Conventional spectra analysis of i) the C₂(d->a) vibrational structure and ii) the CH(B-> X) rotational structure are presented.  Furthermore, spectra  simulations of i) the C₂(d->a) vibrational- structure and ii) the CH(A->X) rotational structure are described.