Combination of upconversion nanocrystals (UCNs) with CeO2 is a decent choice to construct NIR-activated photocatalysts for utilizing the NIR light in the solar spectrum. Herein we present a facile approach to deposit a CeO2 layer with controllable thickness on the plate -shaped NaYF4:Yb,Tm UCNs. The developed core shell nanocomposites display obvious photo catalytic activity under the NIR light and exhibit enhanced activity under the full solar spectrum. For enhancing the separation of photogenerated electrons and holes on the CeO2 surface, we sequentially coat a ZnO shell on the nanocomposites so as to form a heterojunction structure for achieving a better activity. The developed hybrid photocatalysts have been characterized with TEM, SEM, PL, etc., and the working mechanism of such UCN-semiconductor heterojunction photocatalysts has been proposed.