In the wavelength range from 200 up to 1000 nm, optical emission from electronically excited fragments (CN, CH, NH, C-2, H-2, N-2, N-2 (+), and H-Balmer) is detected when aniline plasmas are generated in a multi-dipolar microwave reactor. The optical emission spectrum monitored in very low-pressure conditions (similar to 1 mTorr) shows important characteristics. The H-alpha, H-beta and CN species are the most radiating systems and according to the NH/N-2 intensity ratio, two different operating regimes are observed suggesting a change in the reaction pathways. These two regimes are correlated to changes of the plasma characteristics (electron temperature and density) deduced from Langmuir probe measurements. The plasma thermodynamic state is quantified by implementing numerical simulation codes for synthetic spectra calculations. The rovibrational temperatures (T (r), T (v)) are determined for some neutral species (CN, CH). The obtained values of T (r) and T (v) show the non-local thermodynamic equilibrium of the vibrational and rotational states (T (r) < T (v)). Moreover, the very low pressure aniline-based plasmas deviate substantially from the Boltzmann distribution. Correlation between the optical emission data and the solid phase analysis allows proving that the in situ characterization of the plasma phase is an important predictive tool of physico-chemical properties of the film. From these correlated data, we deduce preponderant chemical reaction pathways which help to better understand the plasma generation. Relative contributions of the dehydrogenation of C-H and N-H groups are established in order to deduce the leading initiation reaction for H-Balmer line formation.