A waveguide coupled surface plasmon sensor for detection of liquid with high refractive index (RI) is designed based on polymer materials. The effects of variation of the thickness of the Au film, polymethyl methacrylate (PMMA) buffer, and waveguide layer on the sensing performance of the waveguide are comprehensively investigated by using the finite difference method. Numerical simulations show that a thinner gold film gives rise to a more sensitive structure, while the variation of the thickness of the PMMA buffer and waveguide layer has a little effect on the sensitivity. For liquid with high RI, the sensitivity of the sensor increases significantly. When RI of liquid to be measured increases from 1.45 to 1.52, the sensitivity is as high as 4 518.14 nm/RIU, and a high figure of merit of 114.07 is obtained. The waveguide coupled surface plasmon RI sensor shows potential applications in the fields of environment, industry, and agriculture sensing with the merits of compact size, low cost, and high integration density.