Environmental concerns, particularly global warming, represent serious threats to public health globally. Metal-organic frameworks (MOFs) are innovative materials with prominent features such as ultrahigh surface area, high porosity and tunable cavities, which make them unique materials both in adsorption of carbon dioxide and catalysis. The design of new nanocomposites by using metal-organic frameworks as building materials has received broad attention recently. Here, nanocrystals of two unique MOF structures (UiO-66 and ZIF-67) were incorporated into electrospun polyvinyl alcohol (PVA) and polystyrene (PS) fibers (noted as MOFibers) by an ex situ method, to transform non-toxic, abundant, economical and renewable CO2 gas to cyclic carbonates in a solvent-free medium. In order to improve the composites' performance, different electrospinning parameters, including applied voltage, flow rate, collection distance, PVA and PS weight fraction in solution, and MOF weight fraction relative to the polymer, were intensively investigated. The synthesized samples were characterized by multiple techniques, such as FTIR, XRD, SEM, UV-vis and TGA, as well as N2 and CO2 adsorption measurement. It was found that all of the composites show properties combining the advantages of MOFs and polymers, such as thermal, chemical, and mechanical stability, structural flexibility, lightweight, adsorption performance and catalytic properties. Additionally, all systems were environment-friendly and the PVA/MOF fibers were easily separated and recycled for consecutive cycles.