Mine tailings can have a specific assemblage of plant species due to their unique physicochemical properties, and this process can be important in developing ecological theory and restoration practice. Physicochemical properties and natural colonization of plants on five lead/zinc (Pb/Zn) mine tailings in southern China were investigated. The tailings studied included Fankou and Lechang in Guangdong Province, and Huangshaping, Shuikoushan, and Taolin in Hunan Province. Physicochemical properties of the tailings varied greatly both among and within tailings ponds, but in general, all contained high concentrations of heavy metals (Pb, Zn, Cu, and Cd) and low concentrations of N, P, and organic matter. Toxic levels of heavy metals and deficiency of major nutrients appeared to be the major constraints for colonization of plants on these Pb/Zn tailings and were reflected in the metal concentration of the plant tissues. The natural colonization of plants on these tailings was limited, with only some small patches distributed mainly on the edge of tailing ponds and even fewer patches on the center of the ponds. In total 54 plant species belonging to 51 genera and 24 families were recorded on the five tailings ponds, of which the 13 species belonging to Gramineae were major components of the tailings’ flora. Species establishing on the tailings at the initial colonization phase greatly depended on their seed-dispersal capacity. Further establishment and growth were then dependent on at least one of the three ecological strategies: (1) microsite (avoidance) strategy: plant establishment on tailings depended on dispersing onto microsites of relatively favorable edaphic conditions; (2) tolerance strategy: plant establishment was a result of evolving metal-tolerant ecotypes or constitutional metal tolerance; and (3) rhizome strategy: plant establishment on tailings depended on clonal growth by rhizomatous extension.