Peripheral functionalization of PAMAM dendrimers with naphthalene units leads to significant ground state aggregation in the system above the critical aggregation concentrations (CAC). Upon photoexcitation of the ground state aggregates, static type excimer formation of naphthalene moiety is observed. Significant red-shifted emission from naphthalene excimers is achieved through generating the static type excimers in polar solvents such as methanol and acetonitrile-water mixtures. Control experiments suggest that the presence of dendritic scaffold in the system play a pivotal role in generating intense static excimer emission in naphthalene modified PAMAM dendrimers, in solution phase at room temperature.