Hollow fiber sorbents are pseudo-monolithic separations materials created with fiber spinning technology using a polymer ‘binder’, impregnated with high loadings of sorbent ‘fillers’[1]. To increase purified gas recovery during the sorption step and to ensure consistent sorption capacity over repeated cycles, a dense, thin polymer barrier layer on the fiber sorbents is needed to allow only thermal interactions between the sorbate loaded layer and the thermal regeneration fluid. This paper considers materials and methods to create delamination-free dual layer fiber sorbents, with a porous core and a barrier sheath layer formed using a simultaneous co-extrusion process. Low permeability polymers were screened for sheath layer creation, with the core layer comprising cellulose acetate polymer as binder and zeolite NaY as sorbent fillers. Appropriate core and sheath layer dope compositions were determined by the cloud-point method and rheology measurements. The morphology of the as-spun fibers was characterized in detail by SEM, EDX and gas permeation analysis. A simplified qualitative model is described to explain the observed fiber morphology. The effects of core, sheath spin dope and bore fluid compositions, spinning process parameters such as air–gap height, spin dope and coagulation bath temperatures, and elongation draw ratio are examined in detail.