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Electrochromic smart windows are promising for building energy savings due to their dynamic regulation of the solar spectrum. Restricted by materials or traditional complementary device configuration, precisely and independently controlling of visible (VIS) and near‐infrared (NIR) light is still on the drawing board. Herein, a novel Zn2+ electrochemically active Ce4W9O33 electrode is reported, which demonstrates three distinct states, including VIS and NIR transparent "bright and warm" state, VIS and NIR opaque "dark and cool" state, VIS transparent and NIR opaque "bright and cool" state. A dual‐operation mode electrochromic platform is also presented by integrating Ce4W9O33/NiO complementary device and Zn anode‐based electrochromic device (Ce4W9O33/Zn/NiO device). Such a platform enables an added VIS opaque and NIR transparent "dark and warm" state, thus realizing four color states through individually controlling Ce4W9O33 and NiO electrodes, respectively. These results present an effective approach for facilitating electrochromic windows more intelligent to weather/season conditions and personal preferences. [ABSTRACT FROM AUTHOR]

Electrochromic smart windows are promising for building energy savings due to their dynamic regulation of the solar spectrum. Restricted by materials or traditional complementary device configuration, precisely and independently controlling of visible (VIS) and near-infrared (NIR) light is still on the drawing board. Herein, a novel Zn 2+ electrochemically active Ce 4 W 9 O 33 electrode is reported, which demonstrates three distinct states, including VIS and NIR transparent "bright and warm" state, VIS and NIR opaque "dark and cool" state, VIS transparent and NIR opaque "bright and cool" state. A dual-operation mode electrochromic platform is also presented by integrating Ce 4 W 9 O 33 /NiO complementary device and Zn anode-based electrochromic device (Ce 4 W 9 O 33 /Zn/NiO device). Such a platform enables an added VIS opaque and NIR transparent "dark and warm" state, thus realizing four color states through individually controlling Ce 4 W 9 O 33 and NiO electrodes, respectively. These results present an effective approach for facilitating electrochromic windows more intelligent to weather/season conditions and personal preferences., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)