Hydrogen (H-2)-selective proton conducting perovskite membrane is the low cost alternative of palladium membrane. In this work, we report the preparation of an A-site deficient Zr-doped proton conductor composition of Ba0.95Ce0.85Tb0.05Zr0.1O3-delta (BCTZ) in the dual-layer hollow fiber configuration consisting of Ni-BCTZ inner porous layer and BCTZ outer dense layer, denoted as BCTZ/Ni-BCTZ hollow fiber via co-spinning, co-sintering, and reduction (in hydrogen) processes. The presence of Zr(4+)in BCTZ perovskite lattice leads to higher CO2 resistance for BCTZ relative to Ba0.95Ce0.95Tb0.05O3-delta (BCT) as revealed by their CO2-temperature programmed desorption results. H-2 permeation flux of dual-layer BCTZ/Ni-BCTZ hollow fiber reaches a maximum of 0.41 mL min (-1) cm (-2) at 900 degrees C. When CO2 was introduced in the permeate side, H (2)permeation flux was enhanced with respect to the CO2-absent case, which is attributed to the presence of reverse water-gas shift reaction that consumes the permeated H-2 to produce carbon monoxide and water. The dual-layer BCTZ/Ni-BCTZ hollow fiber showed stable H-2 permeation fluxes when operated at 800 degrees C in CO2-containing permeate atmosphere for 25 days. Its original morphology and structure were retained following this long term operational test; highlighting its potential use for H-2 separation in CO2-containing reactions and processes.