Ag2S nanoparticles (NPs) emerge as a unique system that simultaneously features in vivo near‐infrared (NIR) imaging, remote heating, and low toxicity thermal sensing. In this work, their capabilities are extended into the fields of optical coherence tomography (OCT), as contrast agents, and NIR probes in both ex vivo and in vivo experiments in eyeballs. The new dual property for ocular imaging is obtained by the preparation of Ag2S NPs ensembles with a biocompatible amphiphilic block copolymer. Rather than a classical ligand exchange, where surface traps may arise due to incomplete replacement of surface sites, the use of this polymer provides a protective extra layer that preserves the photoluminescence properties of the NPs, and the procedure allows for the controlled preparation of submicrometric scattering centers. The resulting NPs ensembles show extraordinary colloidal stability with time and biocompatibility, enhancing the contrast in OCT with simultaneous NIR imaging in the second biological window. In recent years, Ag2S nanoparticles have shown great potential in nanomedicine, specifically in areas such as near‐infrared (NIR) imaging, photothermal therapy, and photoluminescence nanothermometry. In this work, biocompatible and size‐controlled ensembles of Ag2S nanoparticles demonstrate their great dual performance as bright NIR probes and enhancers of the optical coherence tomography signals in ex vivo and in vivo studies.