We report a thermoplasmonically actuated optical modulator based on a liquid–liquid interface decorated with self-assembled Au nanoparticles (Au NPs). The system comprises heptane (top layer) and water (bottom layer), and an Au NPs array at their interfaces. Focused excitation with the plasmonic wavelength (532 nm) generates a localized temperature rise at the interface (
Δ
T
=
3.2
±
0.7
∘
C
), resulting in a thermocapillary flow. We optimized the temperature gradient and the heptane layer thickness so that the resulting thermocapillary flow leads to the formation of a “self-healing hole” at the irradiating zone, which we exploited as an all-optical modulator. A signal beam (655 nm) positioned through the top layer, parallel to the interface, gives a maximum output when the layer is intact (no-hole situation, ON state) and a minimum output when the hole is present (OFF state). Nearly 100% optical modulation is achieved in a reversible manner, highlighting the potential of responsive and reconfigurable fluid–fluid interfaces for optical applications.