The bismuth (Bi )-doped cobalt ferrite nanostructures with dual phase, i.e. cubic spinel with space group Fd3m and perovskite with space group R3c, have been successfully engineered via self-ignited sol-gel combustion route. To obtain information about the phase analysis and structural parameters, like lattice constant, Rietveld refinement process is applied. The replacement of divalent Co by trivalent Bi cations have been confirmed from energy dispersive analysis of the ferrite samples. The micro-structural evolution of cobalt ferrite powders at room temperature under various Bi doping levels have been identified from the digital photoimages recorded using scanning electron microscopy. The hyperfine interactions, like isomer shift, quadrupole splitting and magnetic hyperfine fields, and cation distribution are confirmed from the Mossbauer spectra. Saturation magnetization is increased with Bi -addition up to x = 0.15 and then is decreased when x = 0.2. The coercivity is increased from 1457 to 2277 G with increasing Bi -doping level. The saturation magnetization, coercivity and remanent ratio for x = 0.15 sample is found to be the highest, indicating the potential of Bi -doping in enhancing the magnetic properties of cobalt ferrite.