We use static contact angle measurements and near-edge absorption fine structure to elucidate the surface structure and molecular orientation of hydrocarbon-based mechanically assembled monolayers (H-MAMs), structures formed by combination of assembly of alkyl moieties onto flexible elastomeric substrates and mechanical manipulation of the substrates. Specifically, we report that the organization of the grafted molecular array (“liquid”-like vs. solid-like) can be tailored by varying the degree of stretching of the elastomeric substrate. We also show that the H-MAM surfaces exhibit excellent stability.