Straw biochar is an effective amendment at improving soil aggregate structure and increasing soil carbon and potassium (K) content. However, little information is available on the relationship between soil organic carbon (SOC) and aggregate‐associated K distribution under long‐term biochar application conditions. To address this, a field trial established in 2013 was used to examine the impact of biochar (B0: 0 and B1: 2.625 t ha−1 year−1) and K fertilizer (K0: 0 and K1: 60 kg ha−1 year−1) on the variation in soil aggregate K and reveal the associated influencing factors. A total of four treatments (B0K0, B0K1, B1K0, and B1K1) were included in this study. The soil analysis results obtained in 2021 showed that after 9 years' amendment, B1K1 increased the aggregate exchangeable K (EK) and nonexchangeable K (NEK) pools by 27.40% and 39.55%, respectively, and the increment was primarily because biochar enhanced > 0.25 mm aggregate fractions and strengthened soil K+ adsorption capacity, which benefit from a synergistic increase in SOC and humic acid (HA) content by biochar. 13C NMR analysis showed that long‐term biochar applications altered the chemical composition of SOC, with an outcome of increased aromaticity and hydrophobicity but decreased the lipidation of SOC, indicating that the complexity of SOC molecular structure was enhanced and eventually contributed to strengthening the macroaggregates stability and soil K+ adsorption capacity. The correlation analysis revealed that soil aggregate EK and NEK contents were positively correlated with SOC and HA contents, which further proved that increase of SOC and soil HA is a significant mechanism for biochar ameliorate soil aggregate‐associated K availability.