Controlling the growth, structure and morphology of core-shell nanoparticles (NPs) is significant for catalytic applications and it can be achieved by adding chemical additives to the synthesis reaction mixture. However, achieving precise control over NP synthesis would require a comprehensive understanding of the mechanisms of NP formation under different chemical conditions, which is quite challenging. Here, using in situ liquid cell transmission electron microscopy (TEM), the overgrowth mechanisms of Ag on Au nanobipyramids (NBPs) are studied in AgNO3 aqueous solution with ascorbic acid as the reducing agent. Au-Ag core-shell NPs are formed via two mechanistic modes: (1) atom deposition during which the Ag atoms are deposited directly onto Au NBPs without the addition of poly(vinyl)pyrrolidone (PVP) and (2) nuclei coalescence during which the Ag nanocrystals (NCs) adsorb onto Au NBPs in the presence of PVP. High-resolution imaging reveals the dynamics of the coalescence process of Ag NCs upon addition of PVP. This study helps us to understand the effect of chemical additives during the evolution of a core seed into core-shell NPs with a well-defined composition and shape. It is useful for synthesizing NPs with greater design flexibility and expanding their various technological applications.