Excimer formation in jet-cooled 2-methoxynaphthalene clusters has been investigated by measuring laser-induced fluorescence excitation and dispersed fluorescence spectra. The results show that unlike the dimers of naphthalene and 1-methoxynaphthalene, 2-methoxynaphthalene dimer does not isomerize to excimer configuration from the origin region of the lowest excited state. Excimer emission has been observed only from some of the clusters of size bigger than a dimer. Geometric details of the clusters are considered to be the most important factor for the observed size-dependent behavior in excimer formation dynamics.