We introduce the concept of multipole spatial optical vector solitons associated with higher-order guided modes trapped by a soliton-induced waveguide in a bulk medium. Such stationary localized waves include previously predicted vortex-and dipole-mode vector solitons and also describe new higher-order vector solitons and necklace-type beams. We present the theoretical and experimental results of the structure, formation, and instability development of the quadrupole vector solitons.