A theoretical method to calculate optical emission spectrum emitted from several typical excited diatomic molecular species in plasmas is described based on molecular spectroscopic data, which makes possible to determine the vibrational and rotational temperatures of the molecular species in the plasma. The physical meaning of the rotational temperature is explained as an approximate value of the gas temperatures in plasmas. By the non-equilibrium characteristics in the vibrational or rotational structures, some examples are introduced to understand the excitation kinetics to generate reactive radicals or atoms in the plasmas. The most fundamental method to describe the excitation kinetics of some excited species including atoms is also introduced with the Boltzmann analysis of electrons in the nitrogen and oxygen plasmas.