Fine structure in the α decay of high-spin isomers in 155Lu(25/2−) and 156Hf (8+) has been studied for the first time using αγ -coincidence analysis. Three new α decays from 155Lu(25/2−) and two from 156Hf (8+) have been identified, populating seniority s > 1 states in the N = 82 nuclei 151Tm and 152Yb, respectively. The reduced hindrance factors of the α decays support the previous configuration assignments of the populated states. This is the first observation of states with excitation energy greater than 1.5 MeV being populated following α decay in nuclei outside of the 208Pb region.