We use a microwave field to control the quantum state of optical photons stored in a cold atomic cloud. The photons are stored in highly excited collective states (Rydberg polaritons) enabling both fast qubit rotations and control of photon-photon interactions. Through the collective read-out of these pseudospin rotations it is shown that the microwave field modifies the long-range interactions between polaritons. This technique provides a powerful interface between the microwave and optical domains, with applications in quantum simulations of spin liquids, quantum metrology and quantum networks.