Inverse opal films of molecularly imprinted polymers (MIP) were elaborated using the colloidal crystal template method. The colloidal crystals of silica particles were built by the Langmuir-Blodgett technique, allowing a perfect control of the film thickness. Polymerization in the interspaces of the colloidal crystal in the presence of bisphenol A (BPA) and removal of the used template provides 3D-ordered macroporous methacrylic acid-based hydrogel films in which nanocavities derived from bisphenol A are distributed within the thin walls of the inverse opal hydrogel. The equilibrium swelling properties of the nonimprinted (NIPs) and molecularly imprinted polymers (MIPs) were studied as a function of pH and bisphenol A concentration, while the molecular structures of the bulk hydrogels were analyzed using a cross-linked network structure theory. This study showed an increase in nanopore (mesh) size in the MIPs after BPA extraction as compared to NIPs, in agreement with the presence of nanocavities left by the molecular imprints of the template molecule. The resulting inverse opals were found to display large responses to external stimuli (pH or BPA) with Bragg diffraction peak shifts depending upon the hydrogel film thickness. The film thickness was therefore shown to be a critical parameter for improving the sensing capacities of inverse opal hydrogel films deposited on a substrate.