A novel optical waveguide sensor utilizing surface plasmon resonance (SPR) that enables the measurement of optical absorption and the thickness of a thin film was proposed. A BK-7 glass slide was used as a waveguide core, and an Ag/Au film of 5 mm width and transparent polymethyl methacrylate-co-methacrylic acid (PMMA-co-PMAA) were consecutively deposited to develop the sensor. The PMMA-co-PMAA film was used to control the SPR wavelength. This sensor allows us to measure the optical absorption and thickness of the deposited film using the evanescent wave from the waveguide and the SPR phenomena, respectively. In order to demonstrate this, a layer-by-layer deposit of a film of water-soluble phthalocyanine dye (Alcian blue, pyridine variant, AB) and polystyrenesulfonate was observed. Additionally, adsorptions from a mixed solution of AB and polydiallyldimethylammonium chloride were observed.