Individual electrochemical (EC) impacts of nanoparticles (NPs) on ultramicroelectrode (UME) and optics are coupled to identify chemical processes at the level of individual NPs. While the EC signals characterize the charge transfer process, the optical monitoring gives a complementary picture of the transport and chemical transformation of the NPs. It is illustrated in the case of Ag NP electrodissolution. In the simplest case, the optically monitored individual NP dissolution is synchronized with individual EC spike. Then optics validates in situ the concept of EC nanoimpacts for sizing and counting of NPs. Chemical complexity is introduced from a precipitating agent, SCN-, which tunes the overall electrodissolution kinetics. Particularly, the charge transfer and dissolution steps occur sequentially as the synchronicity between the EC and optical signals is lost. This demonstrates the level of complexity that can be revealed from such electrochemistry/optics coupling.