We report a surprisingly strong ordering of Si-(CH3)(2) groups upon confinement between two surfaces, an oxidized poly(dimethyl siloxane) (PDMSox) elastomer and a methyl-terminated self-assembled monolayer (octadecyltrichlorosilane (OTS)) on sapphire substrates. This enhanced ordering is induced by the template of ordered methyl groups of OTS and is not observed for other surfaces (fluorinated monolayers and sapphire substrates). This strong ordering is reminiscent of layering observed for confined symmetric molecules between two mica surfaces but was expected to vanish between rough macroscopic surfaces. These results provide new insights on confined structure at the interface between two solids and are important in the understanding of surface-controlled processes of practical importance.