The inter-site transition dynamics in a 2D honeycomb lattice of the Mott-insulator Li2irO3 was investigated via broadband time-resolved spectroscopy. Through two excitation regime corresponding to charger transfer (3.1eV) and across Mott-gap excitation (0.8eV), distinct inter-site transition dynamics were revealed and attributed to the distinct photoexcited quasiparticles, i.e., doublon and holon, in the 2D honeycomb lattice.