Here, we report a reaction cascade employing the substituent-induced post-assembly modification of a Co(iii) complex. Unexpectedly, we found that the (triisopropylsilyl)alkynyl moiety introduced to the Sonogashira reaction with the bromo-functionalized Co(iii) assembly plays a "Trojan horse" role, triggering a subsequent, second step of the cascade, i.e. Co(iii) to Co(ii) reduction. The reported substituent-activated Sonogashira-redox cascade reaction might set a new direction in the construction of specific chemical sensors.