Anisotropic polydopamine nanobowls (PDA NBs) show significant promise in biomedicine, distinguished by their unique optical properties and superior cellular uptake compared to spherical nanoparticles. This study presents a novel approach for creating multistimuli‐activated PDA NB‐armored emulsions, encapsulating perfluorohexane (NB‐H) and perfluoropentane (NB‐P) cores, with applications in controlled delivery and ultrasound imaging. Thermal and photothermal activation induced distinct responses in the emulsions, as evidenced by optical microscopy and thermogravimetric analysis. For the first time, neutron scattering techniques (SANS and USANS) under contrast matching conditions are applied to investigate these materials, revealing detailed droplet and microbubble structures and phase transition dynamics. These results show that NB‐H droplets resist phase change under direct heating, whereas NB‐P droplets respond more readily, exhibiting significant bubble formation. During photothermal activation with short near‐infrared (NIR) exposure (15 min at 400 mW cm−2), SANS and USANS analyses reveal varying degrees of phase transition, proving this activation method to be more effective than direct heating. Importantly, NB‐H and NB‐P droplets have excellent ultrasound contrast enhancement and biocompatibility, indicating their potential for contrast‐enhanced ultrasound imaging, theranostics, and photothermal applications. This comprehensive study advances the understanding of multifunctional colloidal materials in biomedicine, contributing essential knowledge to this rapidly evolving field.