Although comprehensive progress has been made in the area of coordination polymer (CP)/metal-organic framework (MOF)-based proton-conducting materials over the past decade, searching for a CP/MOF with stable, intrinsic, high anhydrous proton conductivity that can be directly used as a practical electrolyte in an intermediate-temperature proton-exchange membrane fuel cell assembly for durable power generation remains a substantial challenge. Here, we introduce a new protonconducting CP, (NH4)(3)[Zr(H2/3PO4)(3)] (ZrP), which consists of one-dimensional zirconium phosphate anionic chains and fully ordered charge-balancing NH4+ cations. X-ray crystallography, neutron powder diffraction, and variable-temperature solid-state NMR spectroscopy suggest that protons are disordered within an inherent hydrogen-bonded infinite chain of acid-base pairs (N-H...O-P), leading to a stable anhydrous proton conductivity of 1.45 X 10(-3) S.cm(-1) at 180 degrees C, one of the highest values among reported intermediate-temperature proton-conducting materials. First-principles and quantum molecular dynamics simulations were used to directly visualize the unique proton transport pathway involving very efficient proton exchange between NH4+ and phosphate pairs, which is distinct from the common guest encapsulation/dehydration/superprotonic transition mechanisms. ZrP as the electrolyte was further assembled into a H-2/O-2 fuel cell, which showed a record-high electrical power density of 12 mW-cm(-2) at 180 degrees C among reported cells assembled from crystalline solid electrolytes, as well as a direct methanol fuel cell for the first time to demonstrate real applications. These cells were tested for over 15 h without notable power loss.