Ultrasmall　gold　nanoclusters　(AuNCs)　are　emerging　as　promising　luminescent　nanoprobes　for　bioimaging　due　to　their　fantastic　photoluminescence　(PL)　and　renal-clearable　ability.　However,　it　remains　a　great　challenge　to　design　them　for　in　vivo　sensitive　molecular　imaging　in　desired　tissues.　Herein,　we　have　developed　a　strategy　to　tailor　the　PL　and　biofate　of　near-infrared　II　(NIR-II)emitting　AuNCs　via　ligand　anchoring　for　improved　bioimaging.　By　optimizing　the　ligand　types　in　AuNCs　and　using　Er3+-doped　lanthanide　(Ln)　nanoparticles　as　models,　core-satellite　Ln@AuNCs　assemblies　were　rationally　constructed,　which　enabled　2.5-fold　PL　enhancement　of　AuNCs　at　1100　nm　and　prolonged　blood　circulation　compared　to　AuNCs.　Significantly,　Ln@AuNCs　with　dual　intense　NIR-II　PL　(from　AuNCs　and　Er3+)　can　effectively　accumulate　in　the　liver　for　ratiometric　NIR-II　imaging　of　H2S,　facilitated　by　H2S-mediated　selective　PL　quenching　of　AuNCs.　We　have　then　demonstrated　the　real-time　imaging　evaluation　of　liver　delivery　efficacy　and　dynamics　of　two　H2S　prodrugs.　This　shows　a　paradigm　to　visualize　liver　H2S　delivery　and　its　prodrug　screening　in　vivo.　Note　that　Ln@AuNCs　are　body-clearable　via　the　hepatobiliary　excretion　pathway,　thus　reducing　potential　long-term　toxicity.　Such　findings　may　propel　the　engineering　of　AuNC　nanoprobes　for　advancing　in　vivo　bioimaging　analysis.