Concerning the major factors in the context of excited states analyses, namely charge centroids of the orbitals involved in the excitations, the distance between orbital centroids, and overlap integrals, a new metric-the Ω index-is proposed to assign the character and optical properties of electronically excited states. Using several molecules from different classes and also a well-studied standard database for time-dependent density functional theory (TD-DFT) studies as benchmark criteria, accountability of the developed index is numerically assessed for local, charge transfer, and Rydberg excitations. It is shown that the nature of excited states can be discriminated using the Ω index, where its superior performance for those situations in which the previous descriptors were not helpful is also unveiled. Relationships are also examined between the Ω index and optical properties of some molecules under study in the framework of the sum-over-state approach. It is observed that there are correlations between the proposed index and computed hyperpolarizabilities based on the sum-over-state scheme. These findings offer the possibility of estimating excited-state properties of large systems from simple descriptors without explicitly performing calculations of high-order response functions.