The enrichment of zinc(II) in ammoniacal media with non-dispersive synergistic extraction (NDSX) was achieved in a sandwich-supported liquid membrane module, in which a mixed extractant containing 4-ethyl-1-phenyl-1,3-octadione (HA) and trioctylphosphine oxide (TOPO) was used as the carrier. Several parameters of Zn(II) transport, including carrier concentration, diluent type, feed pH, total ammonia concentration, and temperature, were systematically investigated. The results showed that the mixing of TOPO with HA can effectively improve the Zn(II) enrichment from and into ammoniacal solutions. The transport efficiency of zinc increases with increasing carrier concentration and temperature. Moreover, Zn(II) transport is dependent on the total ammonia concentration and solution pH of the feed phase. The nonpolar n-octane is more beneficial to zinc transport than the polar octanol. Five successive transports exhibit excellent membrane stability and the effective uphill transport of zinc from and into ammoniacal media with NDSX.