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We report a new method for generation of polarization-entangled photon pairs in maximally entangled polarization states. Our approach is based on quantum interference between two polarization states which are non- orthogonal. We present necessary and sufficient conditions for generation the photon pair in a maximally entangled state. The effect of dependence of entanglement on the phase between the interfering states of photons is investigated theoretically and demonstrated experimentally with quantum states produced via spontaneous parametric down-conversion in the double-crystal scheme