Removal of water vapor from humid streams is an energy-intensive process used widely in industry. Effective dehumidification has the potential to significantly reduce energy consumption and the overall cost of a process stream. Membrane-based separations, particularly dehumidification, are an emerging technology that can change the landscape of global energy usage because they have a small footprint, they are easy to scale up, to implement and to operate. The focus of this thesis is to evaluate new directions for the development and use of materials for membrane-based dehumidification processes. It will show advances in the synthesis of new copolymers, a surprising boost in performance with the addition of 2-D materials, propose the use of polybenzimidazole for challenging dehumidification applications, and show how by tuning the nanostructure of a commercially available block copolymer (BCP) it is possible to increase the performance. The design of novel amphiphilic ternary copolymers comprising P(AN-r-PEGMA-r-DMAEMA) allowed selective removal of water vapors from gaseous streams; the effect of varying PEGMA chain length on membrane performance was studied. The membranes showed an excellent performance when the content of the PEGMA segment was 2.9 mol% with a chain length of 950Da. In the mixed-matrix approach, the inclusion of graphene oxide (GO) nanosheets in a different copolymer enhanced the membrane performance by creating selective tortuous pathways for inert gases. The well-distributed GO nanosheets in the defect-free composite membranes resulted in an 8 fold increase in water vapor/N2 selectivity compared to neat membranes. Thirdly, dense polybenzimidazole membranes showed good water vapor permeability, and the addition of TiO2-based fillers with varying chemistry and geometry enhanced the performance of PBI membranes. Lastly, the effect of tuning the morphology of commercially available BCP on dehumidification was demonstrated successfully. The self-assembled morphology formed with cylindrical hydrophobic cores, and the hydrophilic coronas, formed ion-rich highways for fast water vapor transport. Water vapor permeability improved up to 6-fold with the nanostructure modulation more than any membrane reported in the literature. In summary, the work reported in this dissertation has the potential to lay a framework towards tailor-made next-generation membranes aimed for water vapor removal in various dehumidification applications.