Dehumidification is a critical energy-intensive and crucial process for several industries (e.g., air conditioning and gas dehydration). Polymeric membranes with high water vapor permeability and selectivity are needed to achieve an energy-efficient water vapor removal. Herein, we demonstrate high-performance water vapor transport membranes based on novel amphiphilic tercopolymers. A series of amphiphilic tercopolymers comprising polyacrylonitrile, poly(ethylene glycol) methyl ether methacrylate (PEGMA), and poly(N,N-dimethylamino ethyl methacrylate) (PDMAEMA) segments are synthesized via an economical and facile free radical polymerization. The water vapor permeability increases with the increase in PEGMA chain length and the content of PEGMA segments. The best performing membrane (i.e., PEGMA-9502) achieved a water vapor permeability of 174 kBarrer. By optimizing the content and chain length of the PEGMA segments, the membranes could be tuned for carbon capture applications. The optimized membranes tested for CO2 separation showed a high CO2 permeability of 47 Barrer along with CO2/N2 and CO2/CH4 selectivities of 67 and 23, respectively. This work presents a simple and economic amphiphilic tercopolymer for the fabrication of membranes with excellent gas and water vapor separation performance.