We report on the experimental observation of a new type of polarization-locked vector soliton in a passively mode-locked fiber laser. The vector soliton is characterized by the fact that not only are the two orthogonally polarized soliton components phase-locked, but also one of the components has a double-humped intensity profile. Multiple phase-locked high-order vector solitons with identical soliton parameters and harmonic mode locking of the vector solitons were also obtained in the laser. Numerical simulations confirmed the existence of stable high-order vector solitons in the fiber laser.