Input of biomass-derived biochar into soil is recognized as a promising method of carbon sequestration. The long-term sequestration effect of biochar depends on the stability of both its dissolvable and undissolvable fractions in soil, which could be affected by their interactions with soil minerals. Here, walnut shell-derived biochar was divided into dissolvable and undissolvable fractions and then interacted with kaolinite. Stability of kaolinite-biochar associations was evaluated by chemical oxidation and biological degradation. At low dissolvable biochar concentrations, the association was mainly attributed to "Ca2+ bridging" and "ligand exchange", whereas "van der Waals attraction" was dominant at high concentrations. For the undissolvable biochar, kaolinite raised the activation energy of its surface by 22.1%, causing a reduction in biochar reactivity. By chemical oxidation, kaolinite reduced the C loss of total biochar by 42.5%, 33.1% resulting from undissolvable biochar and 9.4% from dissolvable biochar. Because of the presence of kaolinite, the loss of biodegradable C in total biochar was reduced by 49.4% and 48.2% from undissolvable fraction and 1.2% from dissolvable fraction. This study indicates that kaolinite can increase the stability of both dissolvable and undissolvable biochar, suggesting that kaolinite-rich soils could be a beneficial environment for biochar for long-term carbon sequestration.