Hydroxyapatite/collagen composites were prepared in-situ synthesis. The composites were finally achieved by dehydration including air-drying and freeze-drying methods. FTIR, XPS and DSC were employed to investigate the composites dehydrated by two methods. The air-dried composites had better mechanical properties than those of the composites dried by freeze drying. Air-drying of the composite induced more bond formation and crosslink between collagen fibers and HA crystals compared with freeze-drying of the composite, as indicated by the shifting of amide A and I bands to the lower wavenumber and by the changes in the binding energy of O1s, Ca2p, and P2p, leading to the increase of the peak temperature of the composites. Collagen crosslink and bond formation in the air-dried composites were key factors to increase the bending strength of the composites. The results of this study confirm that in situ synthesis and air-dry method are effective ways to obtain nanoHA/COL composites with high mechanical properties.