Solubility-based membrane separation, in which the more soluble species preferentially permeates across the membrane, has attracted considerable recent attention due to both economic and environmental concerns. This solubility-selective mode is particularly attractive over a diffusivity-selective mode in applications in which the heavier species are present in dilute concentrations. Examples include the recovery of volatile organic components (VOCs) from effluent streams and the removal of higher hydrocarbons from natural gas. Recently, nanocomposites have shown great promise as possible membrane materials for solubility-selective separations. The chemical derivatization of inorganic mesoporous substrates has been explored to synthesize organic-inorganic nanocomposite membranes. The most exciting feature of this approach is that it enables the rational engineering of membrane nano-architecture with independent control over the free volume and chemistry to create membranes with highly customizable permselectivity properties. In this study, we synthesized the organic-inorganic nanocomposite membranes by decorating the surfaces of commercially available mesoporous alumina substrates, and surfactant-templated highly ordered mesoporous silicate thin films placed on commercially available macroporous inorganic substrates, with a selective organic material that is physically or chemically anchored to the porous surfaces. Hyperbranched melamine-based dendrimers, with nanometer dimension and chemical composition designed to target certain components, were used as filling agents. We evaluated these membranes for several environmentally relevant separations, such as the recovery of the higher hydrocarbon from air and the removal of trace VOCs from air or water, while exploring the impact of organic oligomer size, chemistry, and surface coverage, as well as substrate pore size and structure, on membrane performance. First, we did a model study to verify the feasibility of dendrimer growth inside mesopores by using ordered mesoporous silica. Alumina-ordered mesoporous silica (alumina-OMS) hybrid membranes were prepared as new inorganic porous substrates. Finally, we synthesized dendrimer-ceramic nanocomposite membranes by growing several generations of melamine-based dendrimers with diverse functional groups directly off the commercial alumina membranes. Composite membranes show very high propane/nitrogen selectivity up to 70.