We report on the first experimental observation of a novel type of optical vector soliton, a dipole-mode soliton, recently predicted theoretically. We show that these vector solitons can be generated in a photorefractive medium employing two different processes: a phase imprinting, and a symmetry-breaking instability of a vortex-mode vector soliton. The experimental results display remarkable agreement with the theory, and confirm the robust nature of these radially asymmetric two-component solitary waves.