After 50 years of its prediction, the highest-lying [2 0 2]3/2 orbit among the six Nilsson single-particle orbits originating from the sd shells in prolately deformed nuclei and the rotational band on this orbit were identified. The band members were observed in 25Al at excitation energies of 6-7.5 MeV in a high-resolution 25Mg(3He,t) charge-exchange reaction at 0 degrees having a strong selectivity for Gamow-Teller transitions. In the comparison with the analogous M1 transitions in 25Mg, the J(pi)=3/2(+) bandhead state and the excited 5/2(+) and 7/2(+) members were clearly assigned.