Islands are paradigms of the pervasive spread of alien plants, but little work has been done assessing pattern and cause of the distribution of such plants in relation to roads on oceanic islands. We studied richness, composition, and distribution of alien plants and compared them with native species along roads on Tenerife (Canary Islands). We studied a single road transect that sampled two contrasting wind-facing aspects (leeward versus windward) and ran from coastal Euphorbia scrubland through thermophilous scrubland to Makaronesian laurel forest at the top of a mountainous massif. We evaluated the effects of elevation, aspect, distance to urban nuclei, and several road-edge features (including road-edge width and management—implying disturbance intensity), using regression models, analysis of variance, and multivariate ordination methods. Richness of both endemics and native nonendemics was explained by elevation (related to well-defined vegetation belts), steepness of the edge slope, and cover of rocky ground. Despite a short elevational gradient (0–650m), we found clear altitudinal zonation by biogeographic origin of both nonendemic natives and aliens, and altitudinal distribution of aliens followed the same zonation as that of natives. Alien species’ richness was related to management intensity determining edge disturbance, road-edge width, and distance to the nearest urban nuclei (propagule sources). Different variables explained distribution patterns of natives, endemics, and aliens along roadsides on leeward and windward aspects. Altitude and aspect also had a strong influence on the frequency of life strategies (woody species, annuals and biennial/perennial herbs) of roadside plant communities. Due to harsher environmental filters operating on the leeward aspect, alien species were distributed along the altitudinal gradient in apparent consistency with general biogeographical affinities. Tropical/subtropical taxa showed exponential decrease with increasing elevation, Mediterranean taxa showed a unimodal response (i.e., maximum richness at mid elevation, minimum at the extremes of the gradient), and temperate taxa showed linear increase with elevation. Native but nonendemic species followed analogous trends to those of aliens. This suggests climatic matching as a prerequisite for successful invasion of this topographically complex island. Other road traits, such as edge width, slope steepness, soil cover, and road-edge disturbance intensity may play a complementary role, at a more local scale, to shape the distribution of alien plants on these island roads.