Crosslinked spherical nanoparticles based on trimethoxysilane monomers have been prepared by polycondensation in aqueous emulsion. These particles have been labeled chemically at their surface region with two different types of organic dye molecules (cinnamate, coumarin), which both are well known for their ability to undergo a reversible photodimerization if irradiated with light of a suitable wavelength. Upon irradiation of dilute solutions of these nanoparticles with UV light, the photodimerization of labels belonging to different colloidal nanoparticles caused the formation of large colloidal clusters consisting of chemically bound individual nanospheres. This process has been quantitatively investigated using light scattering and atomic force microscopy. Importantly, utilizing the reversibility of the photoreaction, the clusters could be broken up by irradiation of the sample with UV light of shorter wavelengths than the light used for their formation.