A series of dendritic ammonium salts have been designed and synthesized. Subsequently, they were used to construct the corresponding [2]rotaxanes by a template-directed clipping approach. Unusually, two unsymmetrical dendritic [2]rotaxanes containing fluorophore (pyrene units) were also obtained; their optical properties, such as UV/vis absorption and fluorescence, were measured. The results indicate that these two rotaxanes possess stronger intermolecular interaction in the solid state than in solution. As a result, solutions of high concentration readily formed the excimer. These special rotaxanes might be applied in dynamic fluorescence-reponsive materials, and the rotaxane structure will also be used as a strategy to adjust the aggregated behaviors of fluorescent molecules.