We report the experimental observation of multiple Bragg diffraction that occurs when the tip of the incident wave vector lies on a line joining the L and W points in the Brillouin zone of a face-centered cubic (FCC) photonic crystal. The multiple Bragg diffraction is analyzed for photonic crystals with different lattice constants and refractive index contrasts. Angle-dependent reflectance spectroscopy indicates strong hybridization of diffraction resonances when the tip of the incident wave vector crosses the W point and the multiple Bragg diffraction is seen to be extended over an angular range of 8 deg around the W point. We also observe a new diffraction resonance in the short-wavelength region for wave vectors shifting toward the W point in the hexagonal facet of the FCC Brillouin zone. Each diffraction resonance is fitted using the Bragg’s law for different planes in the FCC photonic crystal taking into account the internal angle between the planes. The diffraction resonances in the multiple Bragg diffraction regime are assigned to FCC crystal planes with Miller indices (111), (200), (1¯11), and (220). Our results have implications for diverse kinds of wave propagations in periodic structures and applications in light emission, sensing, and structural color pigments.