Composite materials consisting of a monolayer of polystyrene spheres (diameters of 430 and 520 nm) and porous silica, filling in the interstices, have been fabricated and characterized. The proposed growth method introduces some novelties as far as the fabrication of this kind of monolayers is concerned, as it probes the compatibility of coassembly (in which a silica precursor, tetraethyl orthosilicate (TEOS), is added to the base colloid) with confined growth in a wedge-shaped cell, while profiting from the advantages of both techniques. Using this method, it is possible to fabricate the composite monolayer in a single growth step. A systematic study of the influence of TEOS concentration in the initial colloid was performed in order to improve the quality of the two-dimensional crystals produced. Thus, it was demonstrated that the two methods are compatible. Furthermore, the composites were then subjected to thermal treatment so that the polymer is removed to reveal the inverse structure. After the calcination the membranes still present very good quality and so the proposed approach is effective for the fabrication of porous membranes. A comparison of reflectance spectra, between composite monolayers fabricated using this method and composites achieved by infiltrating polystyrene bare opals with silica chemical vapor deposition, is also established. The procedure presented is expected to establish the route for an easier and quicker fabrication of inverse monolayers of high refractive index materials with applications in light control,