High-sensitivity, variable-frequency, high-field electron paramagnetic resonance (EPR) measurements and nuclear magnetic resonance (NMR) measurements are reported for theS=10 single-molecule magnet Fe8Br8. We find that theS=10 state is nested with its first excited state, withS=9, located at only 24±2 K above. Also reported are some preliminary81Br NMR measurements of the unpaired electron spin density on the Br− sites. The results provide new insight and benchmarks for improved electronic and magnetic structural calculations and macroscopic tunneling pathways of this class of single-molecule magnets.