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Photocatalytic H 2 production from methanol is sustainable, yet challenges remain in avoiding carbon-containing gaseous by-products. Titanium silicalite-1 (TS-1) zeolite possesses attractive photocatalytic performance, but lack of modification strategies due to its microporous framework. Herein, we developed a pre-anchoring strategy to confine ultra-small Pt clusters inside TS-1 with ultra-low loading (0.2 mol%), in which Pt were anchored in Ti−OH nests by electronic metal-support interaction (EMSI). The optimal catalyst achieved a remarkable H 2 generation rate of 63.2 mmol g–1 h–1 in CH 3 OH solutions, along with the production of high-value chemical HCHO as the oxidation product with 96.9% selectivity. Investigations reveal that the EMSI between Pt and Ti facilitated the selective decomposition of CH 3 OH to H 2 and HCHO, leading to a nearly zero-carbon-emission process. Accordingly, we propose a light-driven carbon-negative "CO 2 →CH 3 OH→H 2 " route, coupling CO 2 utilization and green H 2 production with CH 3 OH as the intermediate, therefore offering a new perspective for "liquid sunshine". [Display omitted] • Pt clusters were successfully encapsulated inside TS-1 by a pre-anchoring method. • The optimal catalyst achieved a remarkable photocatalytic H 2 generation activity. • HCHO is the main oxidation product with nearly 100% selectivity. • The strong EMSI between Pt and Ti facilitated CH 3 OH decomposition to H 2 and HCHO. • A potential light-driven carbon-negative "CO 2 →CH 3 OH→H 2 " route was proposed. [ABSTRACT FROM AUTHOR]