We use single-spin resonant spectroscopy to study the spin structure in the orbital excited-state of a diamond nitrogen-vacancy center at room temperature. We find that the excited state spin levels have a zero-field splitting that is approximately h
alf of the value of the ground state levels, a g-factor similar to the ground state value, and a hyperfine splitting ~20x larger than in the ground state. In addition, the width of the resonances reflects the electronic lifetime in the excited state. We also show that the spin-splitting can significantly differ between NV centers, likely due to the effects of local strain, which provides a pathway to control over the spin Hamiltonian and may be useful for quantum information processing.
