The replacements of five unique carbons by metal ions within [5,6] fullerene C-70 D-5h has been investigated by using B3LYP/6-31G(d) within 20 isomers of C69M [M = In-, Tl-, Sb+, Bi+] systems. The equilibrium geometrical structures, relative energies, frontier orbitals, and energy gaps for the four considered series are presented. The obtained results indicate a decrease in effective nuclear charge by addition of an electron, and relativistic effects in C69Tl(-) systems causes substantially elongated Tl-C bonds. Variations in the redox characteristics within the four series and among all isomers are expected and also confirmed by Mulliken charges redistributed to neighboring carbon atoms. The vibrational spectra of C69In- and C69Sb+ have been calculated, which could serve as a framework to interpret future experimental results. Our findings show that substitutional doping of C-70 with indium, thallium, antimony, and bismuth ions results in interesting properties which can be utilized in the design, synthesis, and growth of nanomaterials in the future.