Composite adlayer of novel C-60 derivative and BH-PPV was constructed on Cu(111) electrode surfaces in solution. First, hexa(sulfobutyl)C-60 and BH-PPV adlayers were prepared, respectively. Then, adding another molecule resulted in the formation of a composite adlayer, demonstrated by cyclic voltammetry, UV-visible spectra, and in situ STM. All of these molecules form well-ordered adlayers. Their molecular features clearly appeared in high-resolution STM images. The electronic properties of these molecular adlayers were studied by using a capillary tunnel junction method. The I-V characteristics show different nonlinear behavior for the three adlayers. The present results provide a concrete example of the systematic design of self-organized layers with promising properties and demonstrate that controllable layer by layer composite film can be constructed at liquid/solid interface at room temperature.