We investigated the energetic, structural and electronic properties of a N4 cavity doped C60 fullerene (C54N4), and its transition metal (TM = Ti, Cr, Fe, Ni, and Zn) decorated complexes using density functional theory calculations. The computed formation energy for C54N4 is about −156.1 kcal/mol, which is slightly less negative than that of C60 (−161.0 kcal/mol). The electrical conductivity, and work function of C60 are increased by N4 doping. The TM-C54N4 bond includes a synergistic interaction between a σ-type donation, and π-type back-bonding. The TM@C54N4 complexes possess a ground state electron distribution with a spin multiplicity which equals that of the free TM atom. The stability of the complexes are as follows: Cr > Ti > Ni > Fe > Zn depending on the effective nuclear potential, and electronic configuration of the TM atoms. The decoration energy is inversely related to the experimental first ionization potential energy of the TM atoms. All TM@C54N4 indicate higher electrical conductivity compared to the bare C54N4 and by increasing the atomic number of TM, the electrical conductivity is increased. Also, the work function of C54N4 nanocluster significantly decreases by TM decoration which reduces the emitted electron current density from the surface of C54N4 nanocluster.