In this work, porous HAP nanofibers assembled from nanorods were developed as potential devices for the treatment of Cu(II), Cd(II), and Pb(II) contamination of consumable waters. Two steps were employed in the HAP nanofibers fabrication. First, rod-like HAP nanoparticles were synthesized through a chemical pathway from Ca(NO₃)₂·4H₂O, (NH₄)₂HPO₄, and polyvinylpyrrolidone (PVP) as a capping agent. The subsequent electrospinning was performed to fabricate the PVP/HAP hybrid nanofibers as precursors to obtain pure HAP nanofibers assembled from nanorods via a calcination process. The effects of PVP dosage on morphology was investigated. And a possible formation mechanism of rod-like HAP was proposed. Then the removal efficiency of porous HAP nanofibers toward Cu(II), Cd(II), and Pb(II) were evaluated via sorption kinetics and sorption isotherms. Our results proved that the sorption kinetic data were well fitted by the pseudo second-order rate equation, and the adsorption of Cu²⁺, Cd², and Pb²⁺ ions on HAP nanofibers correlated well with the Langmuir equation as compared to Freundlich isotherm equation under the concentration range studied. These novel porous HAP nanofibers assembled from nanorods promise a feasible advance in the development of new, easy to handle, and low-cost water purifying methods.