Cross sections for the charge-exchange reaction (d,2He) on 50V, the only odd-odd stable nucleus in the pf shell, have been measured at an incident energy of 171 MeV. The two correlated protons of the unbound 2He system were both momentum analyzed and detected by the same spectrometer and detector. Measurements have been carried out at forward center-of-mass angles up to 6�. The GT+ strength distribution has been extracted up to about 12 MeV of excitation energy. Because charge-exchange reactions from 50V provide a unique opportunity to probe Gamow-Teller response from an odd-odd nucleus of the pf shell, the present study serves as important test case for model calculations and astrophysical processes that proceed through GT-type transitions. Consequently, the experimental result is compared with a large-scale shell-model calculation, and the implications for electron-capture processes in presupernova environments are discussed.