The study of the ionization process of molecules in an intense infrared laser field is of paramount interest in strong-field physics and constitutes the foundation of imaging of molecular valence orbitals and attosecond science. We show measurement of alignment-dependent ionization probabilities of the lower-lying orbitals of the molecules by experimentally detecting the alignment dependence of fluorescence emission from tunnel ionized carbon dioxide molecules. The experimental measurements are compared with the theoretical calculations of the strong field approximation and molecular Ammosov-Delone-Krainov models. Our results demonstrate the feasibility of an all-optical approach for probing the ionization dynamics of lower-lying orbitals of molecules, which is until now still difficult to achieve by other techniques. Moreover, the deviation between the experimental and theoretical results indicates the incompleteness of current theoretical models for describing strong field ionization of molecules.