The dynamic growth of the insurance market has directly contributed to the increased role played by toxicological analysis, in combination with medico-legal expert opinions, in determination of the scope of liability of insurers with respect to the insured. Contractual exemptions of the insurer’s liability do not cover all medical and toxicological aspects and do not provide for many possible events for which toxicological investigations and related medico-legal expert opinions may provide important premises in the assessment of the scope and nature of the insurer’s liability. Practice shows that a substantial number of insurance companies have not developed rules of claims processing capable of excluding the possible effect of xenobiotics at the time of the event, which could give grounds for exemption from liability. Insurance companies cannot single-handedly resolve issues that require special expertise supported by various forms of toxicological analysis. This paper demonstrates that medico-legal toxicology can be a useful tool in the protection of the interests of insurance companies, especially when it is supported by a medico-legal expert opinion.