Porphyrin-fullerene dyads are representative class of donor-acceptor molecular systems capable of undergoing photoinduced charge separation, the phenomenon that is the key process in solar energy conversion systems either in organic solar cells or photoredox catalysis. The charge-separated state generated in covalently linked dyad is a highly polarized electronically excited state. Formation of this state typically proceeds as a result of the relaxation of a locally excited state of higher energy, which is populated upon the initial excitation of the dyad. The review of computational and spectroscopic studies of the excited states in porphyrin-fullerene covalently linked dyads is given in the present chapter.