We show that a comparison of the depletion spectra of Na-n(+) (n=2-9,11,21) clusters recorded at low temperature and optically allowed transitions determined for the stable structures using ab initio methods accounting for electron correlation allows the assignment of the cluster geometry to the measured features. Due to the large mobility of atoms in alkali metal clusters, the influence of temperature on structural and electronic properties is significant. The lowering of temperature reveals new spectroscopic features which are structure dependent. Optical response properties of small cationic Na-n(+) clusters are characterized by rich molecularlike spectroscopic patterns, also with increasing size, and differ substantially from those found for neutral clusters. It has been clearly demonstrated that not only the number of valence electrons but its mutual interplay with the geometric properties determine optical response features.