We report on the optical characterization of three-dimensional opal-like photonic crystals made by self-organized nanospheres of poly[styrene-(co-2-hydroxyethyl methacrylate)] having a face centred cubic (fcc) structure oriented along the [111] direction. A detailed optical characterization of the samples is presented using angle resolved reflection spectroscopy in specular geometry. The investigated energies are between a/lambda=0.5 and a/lambda=1.5 (where a is the lattice parameter and lambda is the light wavelength), a region in which both first and second-order Bragg diffraction are expected. Some interesting features as branching of the Bragg peak dispersion and high energy reflection peaks are revealed. We compare the experimental data with theoretical calculations using both Bragg diffraction and band structure approach. A comparison with recent results reported in the literature is also presented.