Ionization energies and electron affinities of Scr-androstane and seven of its derivatives were calculated with the semiempirical HAM/3 method. Observed photoelectron spectra in the literature were assigned using the calculated ionization energies. Good agreement (within an average error of about 0.2 eV) between theory and experiment for ionization events that originate from non-bonding orbitals of carbonyl oxygens and a orbitals in C=C bonds were found. However, an error of as much as 1.4 eV was found in the calculated ionization energy of 5 alpha-androstane, in which only sigma-type orbitals exist.39141671169178