A hybrid polymer/inorganic membrane with dual transport pathways overcomes traditional limitations. The inorganic phase consists of a metal-organic framework (MOF), which is an ideal inorganic dispersant to construct dual transport pathways as the crystalline porous structure of MOFs is more amenable to molecular diffusion than polymers. Previous hybrid membrane research has failed to achieve sufficiently high loadings to establish a percolative network necessary for dual transport, often due to mechanical failure of the membrane at high loading. Using polysulfone and UiO-66-NH2 MOF as a model system, we achieve high MOF loadings (50 wt %) and observe the evolution from single mode to dual transport regimes. The newly formed percolative pathway through the MOF acts as a molecular highway for gases. As the MOF loading increases to 30 wt %, CO2 permeability increases linearly from 5.6 barrers in polysulfone homopolymer to 18 barrers. Crucially, between 30 and 40 wt %, a percolative MOF network arises and the CO2 permeability dramatically rises from 18 to 46 barrers; an eight-fold increase over pure polysulfone, while maintaining selectivity over methane and nitrogen near the pure polymer at 24 and 26, respectively.