The objective of this work is to find relations between adherence and friction behaviors of elastomer networks. The chosen approach is based on the parallel study of the initial molecular weight (i.e., the degree of cross-linking) dependence of both adherence and friction. The polymers used are cross-linked polydimethylsiloxane (PDMS) and the substrate is a smooth glass plate. The experimental procedure uses both friction (pin on disk tribometer) and adhesion (tack test) measurements, associated with surface analysis and mechanical and rheological characterizations. Tack results show that high molecular weight PDMS exhibits the greater adherence energy. This can be explained by the role of both chain length and free and pendant chains: more numerous and longer free chains favor the substrate wetting (at a molecular scale) and increases the energy dissipation during separation (extraction and reptation mechanisms). However, friction results indicate a higher friction resistance for low molecular weight PDMS. This result could be quite surprising. An explanation based on interfacial sliding properties of free and pendant chains can be proposed. Elsewhere, for the lower molecular weight polymer, elastic contact present during friction is able to act as a forced wetting, constraining the network and consequently leading to a greater energy dissipation.