Knowles will appear in a series of European TV ads for the brand.
Samsung's Ultra Music TV commercial will air in April in Europe and gradually expand to other countries where the Ultra Music Samsung model is available. The phone will come with Knowles' hit 'Irreplaceable' pre-loaded on the handset.
Geesung Choi, president of Samsung Electronics' Telecommunications Business, said: "We are thrilled to be working with Beyonce because we have a lot in common - we both have a strong passion for music, video and entertainment and we are considered icons in our respective industries. We both aspire to deliver seamless satisfaction and bring music to life."
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