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We consider exciton-photon coupling in semiconductor microcavities in which separate periodic potentials have been embedded for excitons and photons. We show theoretically that this system supports degenerate ground-states appearing at non-zero inplane momenta, corresponding to multiple valleys in reciprocal space, which are further separated in polarization corresponding to a polarization-valley coupling in the system. Aside forming a basis for valleytronics, the multivalley dispersion is predicted to allow for spontaneous momentum symmetry breaking and two-mode squeezing under non-resonant and resonant excitation, respectively.