A b initio local spin density method has been used to investigate chemical bonding of aluminum with polyimide surfaces. We focused in this work on the carbonyl group, which is, as demonstrated by x-ray photoelectron spectroscopy (XPS) and high-resolution electron energy loss spectroscopy (HREELS), the active site, at least at low metal coverage. We found that the formation of a linear complex C–O–Al is favored over other positions in the vicinity of carbonyl group. The vibrational frequency corresponding to oxygen–aluminum stretching is calculated and compared with HREELS data. We also calculated core level chemical shifts. The agreement with XPS results is satisfactory. Finally, we suggest a mechanism for the adsorption of Al on polyimide surfaces.