The pH-dependent adsorption of perchlorate (ClO4(-)) by wood-derived biochars produced at 200-700 °C (referred as FB200-FB700) was investigated to probe the anion retention mechanisms of biochars and to identify the interactions of water and biochar. ClO4(-) adsorption was controlled by the surface polarities and structural compositions of the organic components of biochars, rather than their inorganic mineral components. FB500-FB700 biochars with low polarity and high aromaticity displayed a superior ClO4(-) adsorption capacity, but which was affected by solution pH. Besides electrostatic interaction, hydrogen bonding to oxygen-containing groups on biochars was proposed the dominant force for perchlorate adsorption, which led to the maximum adsorption occurring near pHIEP, where surface charge equals zero. The dissociation of these surface oxygen-containing groups was monitored by zeta potential curves, which indicated that the H-bonds donors on biochar surface for ClO4(-) binding were changed from -COOH (ClO4(-)···HOOC-) and -OH (ClO4(-)···HO-) to -OH alone with an increase in pH. The H-bond force was strengthened by the condensed aromatic surfaces, since high temperature biochars provided a hydrophobic microenvironment to accommodate weakly hydrated perchlorate and facilitated the H-bonds for ClO4(-) binding to functional groups by the large π subunit of their aromatic substrate. Lastly, the batch and column tests of ClO4(-) adsorption showed that biochars like FB700 are effective adsorbents for anion pollutant removal via H-bonding interaction.