When designing dyes for dye-sensitized solar cells (DSCs), it is highly important to consider each of electron transfer (ET) processes within the device. The overall conversion efficiency will greatly decrease if the ET rates interconnecting these processes are inefficient or unbalanced. We studied these ET behaviors by using first-principle calculations. The established TDDFT methods in combination with Mulliken charge analysis have been applied to probe intramolecular charge transfer (ICT) excitations within the dye as well as their tendency toward dye regeneration. These can be broadly applied to dipolar organic dyes and zinc (II) porphyrin dyes. Extensive study has also been carried out on theoretically determining the rates of charge recombination (kCR) reactions explicitly via calculating electronic coupling and the value of −(λ+ΔG) prompted by Marcus electron transfer theory.