We examine whether firms with high organization capital (OC) are more likely to purchase Directors’ and Officers’ (D&O) liability insurance, using a panel of Chinese A-share listed companies from 2009 to 2021. We document a robust positive association between OC and the propensity to carry D&O insurance. The effect remains statistically and economically significant after controlling for firm characteristics and employing multiple identification strategies to address endogeneity. We propose two economic channels through which OC affects D&O insurance demand, namely, agency and information asymmetry. Consistent with these mechanisms, we find that the positive OC–D&O relationship is significantly stronger in firms with weaker internal governance and those facing opaquer information environments. Additional cross-sectional analyses show that this effect is concentrated in privately-owned firms and in regions with more developed market institutions, suggesting that external pressures accentuate the value of insuring key decision-makers. Our results are robust to alternative model specifications and remain stable after using propensity score matching, instrumental variable approaches, and the Heckman two-stage model. Overall, the findings highlight OC as a critical internal driver of corporate insurance decisions. Firms with substantial intangible assets strategically obtain D&O coverage to strengthen governance and reduce information frictions, especially in emerging markets like China where formal investor protections are still evolving.