When tested in solar cells, ruthenium polypyridinic dyes with extended pi systems show an enhanced light-harvesting capacity that is not necessarily reflected by a high (collected electrons)/(absorbed photons) ratio. Provided that metal-to-ligand charge transfer bands, MLCT, are more effective, due to their directionality, than intraligand (IL) pi-pi* bands for the electron injection process in the solar cell, it seems important to explore and clarify the nature of the absorption bands present in these types of dyes. This article aims to elucidate if all the absorbed photons of these dyes are potentially useful in the generation of electric current. In other words, their potentiality as dyes must also be analyzed from the point of view of their contribution to the generation of excited states potentially useful for direct injection. Focusing on the assignment of the absorption bands and the nature of the emitting state, a systematic study for a series of ruthenium complexes with 4,4'-distyryl-2,2'-dipyridine (LH) and 4,4'-bis[p-(dimethylamino)-alpha-styryl]-2,2'-bipyridine (LNMe2) "chromophoric" ligands was undertaken. The observed experimental results were complemented with TDDFT calculations to elucidate the nature of the absorption bands, and a theoretical model was proposed to predict the available energy that could be injected from a singlet or a triplet excited state. For the series studied, the results indicate that the percentage of MLCT character to the anchored ligand for the lower energy absorption band follows the order [Ru(deebpy)(2)(LNMe2)](PF6)(2) > [Ru(deebpy)(2)(LH)] (PF6)(2) > [Ru(deebpy)(LH)(2)](PF6)(2), where deebpy is 4,4'-bis(ethoxycarbonyl)-2,2'-bipyridine, predicting that, at least from this point of view, their efficiency as dyes should follow the same trend.