SHG (second harmonic generation) interferometry and linear dichroism measurements were applied to the characterization of Langmuir-Blodgett monolayers composed of rhodamine B derivatives on hydrophilic fused silica substrates, When excited with a Nd-YAG laser, the contribution of dimeric species composed of rhodamine B chromophores to the nonlinear optical behavior was large, even though the relative concentration of the dimers was small. This implies the formation of noncentrosymmetrically oriented dimers with a relatively higher nonlinear molecular susceptibility, B. Therefore, a unique phenomenon was observed; that is, the relative phase of the SH light shifted depending on the incident light polarization (p and s). In addition, it was found that the relatively standing up orientation was favored for the dimer, while a strongly tilted orientation was favored for the monomer.