We show several suitable modifications in π-conjugation paths of buckyferrocenes (face-to-face fusion of ferrocene and modified fullerene fragments). Interestingly, these modifications substantially affect their topologies, spin densities, diradical characters as well as nonlinear optical (NLO) properties. We study the topological dependence of open-shell diradical character and second hyperpolarizability (γ), the third-order NLO properties at the molecular scale, in several buckyferrocenes. On the basis of their different diradical characters (yi), these buckyferrocenes are categorized into three groups, i.e., closed-shell (yi = 0), intermediate open-shell singlet (0 < yi < 1), and almost pure open-shell singlet (yi = 1) compounds. For example, we found that buckyferrocenes including (CpFe)2 η5C60Me10 and (CpFe)2η5C70Me10 have closed-shell configurations. The buckyferrocenes (CpFe)2η5C60, (CpFe)2η5C70, (CpFe)2η5C70Me8, (CpFe)2η5C70Me4 and (CpFe)2η5C30 are intermediate open-shell singlet, while (CpFe)2η5C60Me4 and (CpFe)2η5C60Me8 are pure open-shell singlet complexes. Interestingly, the γzzzz amplitude of (CpFe)2η5C60, an open-shell intermediate diradical complex, is about 41 times and 13 times as large as those of its closed-shell ((CpFe)2η5C60Me10) and pure diradical ((CpFe)2η5C60Me8) counterparts, respectively. The fact that larger γzzzz values are obtained for buckyferrocenes with intermediate diradical characters is in line to the “y-γ correlation” obtained from the valence configuration interaction (VCI) results for a two-site diradical model as well as for fullerene and graphene systems. The γzzzz density analysis shows that the large positive contributions originate from the large γzzzz density distributions on the upper- and lower-extended edges of the buckyferrocenes, between those significant spin polarizations appear within the spin-unrestricted DFT level of theory. These results demonstrate that such buckyferrocenes are potential candidates for a novel class of open-shell singlet NLO systems, where γzzzz values are modulated tuning their diradical character through the use of suitably modified fullerene fragments.