The adsorption structure and binding of maleimide (MI) and succinimide (SI) on silver nanocolloidal surfaces have been comparatively investigated by means of pH-varied surface-enhanced Raman scattering (SERS). The two molecules appeared not to adsorb onto Ag surfaces at pH values below 5. The appearance of a ring ν (CH) band at ~3100 $cm^{-1}$ denoted the standing geometry of MI’s aromatic ring on Ag. The absence or weakness of in-plane vibrational modes of MI and SI also supported a perpendicular orientation of MI and SI on Ag from the electromagnetic selection rule. Density functional theory (DFT) calculations were employed to examine the vibrational frequencies of MI’s and SI’s neutral and anionic states.