According to our scheme to construct quantum phase transitions (QPTs) in spin chain systems with matrix product ground states, we first successfully combine matrix product state (MPS) QPTs with spontaneous symmetry breaking. For a concrete model, we take into account a kind of MPS QPTs accompanied by spontaneous parity breaking, though for either side of the critical point the GS is typically unique, and show that the kind of MPS QPTs occur only in the thermodynamic limit and are accompanied by the appearance of singularities, diverging correlation length, vanishing energy gap and the entanglement entropy of a half-infinite chain not only staying finite but also whose first derivative discontinuous.