Methylamine adsorption on the ordered Ni3Al(111) and NiAl(110) surfaces has been investigated by high resolution photoelectron spectroscopy and density functional theory calculations. Methylamine adsorbs molecularly at both surfaces at low temperature (90 K). The experiments show that methylamine interacts with the surface aluminium atoms on both surfaces, resulting in a positive binding energy shift relative to the Al 2p bulk contributions. A shift towards lower binding energy is also observed on NiAl(110) attributed to first and second layer surface Al atoms not bonded to methylamine. According to total energy calculations methylamine binds through its N atom to Al on-top sites on NiAl(110) while the Ni on-top site is found to be slightly preferred over the Al on-top site on Ni3Al(111). Calculated adsorbate induced shifts are, however, in good agreement with the experimental values only when methylamine is situated in the Al on-top site on both surfaces. In both cases, a lone pair bonding mechanism is found.