A Langmuir layer of ultrafine platinum particles (2-6 nm in diam) has been developed on a water surface by dropping a Pt colloid solution, prepared by refluxing an ethanol-water (1:1) solution of hexachloroplatinic(IV) acid in the presence of poly(N-vinyl-2-pyrrolidone) as a stabilizer. The layer is transferred onto a single-crystal n-type silicon (n-Si) wafer by the horizontal lifting method. The Pt particles are rather homogeneously scattered on n-Si, and the particle density can be controlled on a nanometer scale by changing the area of the Langmuir layer at the time of transfer. The open-circuit photovoltage (V(oc)) for photoelectrochemical (PEC) solar cells with such n-Si electrodes is inversely related to Pt-particle density, and reaches 0.635 V, much higher than that for n-Si coated with a continuous Pt layer (ca. 0.30 V) or that for the conventional p-n junction Si solid solar cell of a similar simple cell structure (ca. 0.59 V). This result is in harmony with our previously proposed theory, the above increase in V(oc) being explained by the decrease in the majority carrier dark saturation current density.