The bonding and reactions of adsorbed aniline have been characterized on the Ni(100) surface both in hydrogen and in vacuum with a combination of surface spectroscopies. The structure of adsorbed aniline and derived intermediates has been characterized by near-edge X-ray absorption fine structure (NEXAFS) and X-ray photoemission spectroscopy (XPS). The dominant surface reactions have been studied using temperature-programmed reaction spectroscopy (TPRS) and in-situ temperature-programmed fluorescence yield near-edge spectroscopy (TP FYNES). Competition between hydrogenation, hydrogenolysis, and dehydrogenation of aniline in the 300-400 K temperature range depends markedly on hydrogen pressures in the vacuum to 0.01 Torr range. In the absence of external hydrogen, dehydrogenation dominates with increasing temperature. Both hydrogenation and hydrogenolysis of aniline-derived surface intermediates are enhanced dramatically by hydrogen atmospheres. For aniline coverages up to 1 monolayer, hydrogenolysis to form benzene at 475 K is dominant over a broad hydrogen pressure range (> 10(-6) Torr). Ultrasoft X-ray absorption spectra above the carbon K edge of the aniline-derived surface intermediates reveal that the precursor for hydrogenolysis is a hydrogenated aniline-derived species indistinguishable from cyclohexylamine. In the presence of hydrogen, C-N bond activation appears to be correlated with unexpectedly large tilt angles near 55 degrees observed at the hydrogenolysis temperature. In the absence of hydrogen atmospheres, low-temperature loss of amino hydrogen causes the ring to reorient even further away from the surface and therefore remain aromatic with increasing temperature. Both the resonant stabilization of the C-N bond and reorientation of the C-N bond away from the surface contribute to decreased C-N bond activation in the absence of external hydrogen.