We have observed large tunneling Magnetoresistance (TMR) in amine functionalized octahedral nanoparticle assemblies. Amine monolayer on the surface of nanoparticles acts as an insulating barrier between the semimetal Fe3O4 nanoparticles and provides multiple tunnel junctions where inter-granular tunneling is plausible. The tunneling magnetoresistance recorded at room temperature is 38% which increases to 69% at 180 K. When the temperature drops below 150 K, coulomb staircase is observed in the current versus voltage characteristics as the charging energy exceeds the thermal energy. A similar study is also carried out with spherical nanoparticles. A 24% TMR is recorded at room temperature which increases to 41% at 180 K for spherical particles. Mössbauer spectra reveal better stoichiometry for octahedral particles which is attainable due to lesser surface disorder and strong amine coupling at the facets of octahedral Fe3O4 nanoparticles. Less stoichiometric defect in octahedral nanoparticles leads to a higher value of spin polarization and therefore larger TMR in octahedral nanoparticles.