Provided is a process for production of composite fine particles with heterogeneous surfaces. The process ensures a high productivity and enables a voluntary control of particle diameters. Further, the process imposes no restrictions on heterogeneous substances added for functional expression, and allows a heterogeneous substance to be encapsulated in central portions of composite fine particle spheres. A composite film obtained by laminating two or more kinds of films is cut into minute pieces, followed by melting the same to obtain spherical minute pieces. Particularly, liquid films are separately formed with two or more kinds of liquids containing polymerizable monomers. Further, two or more kinds of films can thereby be obtained through polymerization. The two or more kinds of films thus obtained are then laminated to further allow polymerization to take place, thus obtaining the composite film.