We introduce monotitanium-based endohedral metallofullerenes (EMFs) using density functional theory calculations. Isomeric C-64 fullerenes are initially employed as hosts, and Ti@C-64 species show novel features on the electronic structures. Energetically, the preference of titanium residing on triple fused -pentagon subunits is proposed in theory. More importantly, different from current knowledge on mono-EMFs, electron transfer between titanium and carbon cages is not unified but is essentially dependent on the pentagon distribution of the binding sites, giving rise to variations of the cationic titanium of Ti@C-64. Such selective electron-transfer character is extended to the study of the encapsulation of other neighboring metal atoms (i.e., calcium and scandium). Because of their different capabilities to accept d electrons, fullerene cages with distinct fused pentagon motifs show selective metal encapsulation characters. In addition, some other fullerenes (C-44-C-48 and C-82) are selected as hosts to study the electron transfer behavior of titanium in smaller fullerenes and larger systems without pentagon adjacency.