A 2×2 optical waveguide coupler at 850 nm based on the multimode interference (MMI) structure with the polysilsesquioxanes liquid series (PSQ-Ls) polymer material and the imprint technique is presented. The influence of the structural parameters, such as the single mode condition, the waveguide spacing of input/output ports, and the width and length of the multimode waveguide, on the optical splitting performance including the excess loss and the uniformity is simulated by the beam propagation method. By inserting a taper section of isosceles trapezoid between the single mode and multimode waveguides, the optimized structural parameters for low excess loss and high uniformity are obtained with the excess loss of -0.040 dB and the uniformity of -0.007 dB. The effect of the structure deviations induced during the imprint process on the optical splitting performance at different residual layer thicknesses is also investigated. The analysis results provide useful instructions for the waveguide device fabrication.