The adhesion properties of polychloroprene can be improved by addition of such materials as piperylene-styrene co-polymer (PSC), VeoVa-10 polymer, VeoVa-11/methyl methacrylate/2ethylhexyl acrylate co-polymer (VeoVa-11/MMA/2EHA) and poly(vinyl acetate) waste (wPVAc). Here, the relationship between adhesion properties and surface tension of polychloroprene was investigated. Contact angle measurements have been used to study the effects of nature and content of polymeric additives on the adhesion and surface properties of polychloroprene. Low-surface-tension VeoVa-10 polymer has the tendency to migrate to the surface of polychloroprene; thus, adhesion is determined mainly by this additive property. Enrichment of polychloroprene film bottom layer by the additive was observed using high-surface-tension PSC and wPVAc. In this case, the adhesion properties of polychloroprene depend on the interactions at the interface. Adhesion properties of polychloroprene were found to depend not only on compatibility between adhesive components, but also on compatibility between the adherend and the adhesive.