In this work, we demonstrate the measurement of the Brillouin gain spectra of vector modes in a few-mode fiber for the first time using a simple heterodyne detection technique. A tunable long period fiber grating is used to selectively excite the vector modes supported by the few-mode fiber. Further, we demonstrate the non-destructive measurement of the absolute effective refractive indices (n eff ) of vector modes with ~10-4 accuracy based on the acquired Brillouin frequency shifts of the modes. The proposed technique represents a new tool for probing and controlling vector modes as well as modes carrying orbital angular momentum in optical fibers with potential applications in advanced optical communications and multi-parameter fiber-optic sensing.