A new adsorbent for removing heavy metal lead ions from wastewater, poly(vinyl alcohol)/hydroxyapatite (PVA/HAp) composite cryogel, has been investigated. The PVA/HAp cryogel was prepared through a clean process by using water and freeze-thawing. The PVA/HAp cryogel is provided with interconnected macropores varying from 0.1 um to several um and well dispersed and immobilized HAp in cryogel. Continuous column tests of lead ion sorption were carried out to test the sorption ability of PVA/HAp cryogel. Moreover, it was found that the porosity of the cryogels was increased by adding water-soluble poly(vinyl pyrrolidone) (PVP) followed by its extraction after cryogellation. The maximum sorption capacity of the cryogels was 69 mg/g HAp for the cryogel having 20 wt% of HAp based on PVA. On the other hand, the maximum capacity was increased to 108 mg/g HAp when 15 wt% PVP based on PVA was added and extracted due to the increase of the effective HAp amount exposed to the aqueous lead ion.