Cation-selective microcontact printing (mu CP) is achieved by the combination of a surface-molecular-imprinted layer-by-layer (SMILbL) film with mu CP. The SMILbL film greatly enhances the charge selectivity of the imprinted-film-modified stamp and the PDMS stamp modified by the SMILbL film shows a high selectivity to multiply charged cations. The SMILbL-film-modified stamp can also be used for selective transfer of single-charged chemical species.