The dynamics of bubbles near a liquid–liquid interface represent a complex multiphase problem with numerous potential applications. This paper utilizes pulsed laser-induced microbubbles at the liquid–liquid interface to achieve the multi-orifice ejection of liquid metal microdroplets that are challenging to achieve with traditional inkjet printing. The study combines the expansion and collapse processes of thermal bubbles at the two-phase liquid interface with the ejection process of liquid metal droplets, unveiling the underlying mechanisms of liquid metal droplet ejection. In this work, the influence of laser parameters on the behavior of thermal bubbles at the liquid–liquid interface and the double-peak pressure effect was investigated. The impact of laser parameters on the ejection behavior of liquid metal droplets was also examined, which provides theoretical support for the wide applications of bubble dynamics at the liquid–liquid interface in the field of liquid metal inkjet printing.