Atmospheric　water　harvesting　(AWH)　offers　an　appealing　way　to　mitigate　the　shortage　of　clean　water.　Despite　the　significant　advances　of　AWH,　unexpected　sorbent　leakage　and　inferior　waste　heat　management　are　two　long-standing　bottlenecks　for　its　practical　application.　Herein,　a　core-shell　structural　cellulose　nanofiber　aerogel　(Core-Shell@CNF)　is　proposed　by　loading　lithium　chloride　(LiCl)　in　the　hydrophilic　core　and　confining　it　in　the　hydrophobic　shell.　The　distinct　wettability　difference　between　the　core　(hydrophilic)　and　the　shell　(hydrophobic)　allows　the　programmable　free　transport　of　the　water　molecules　but　prevents　the　leakage　of　the　LiCl　solution,　achieving　continuable　and　recyclable　water　sorption/　desorption.　Moreover,　the　Core-Shell@CNF　exhibits　fast　sorption　desorption　kinetics　enabled　by　the　vertically　aligned　pores　of　the　CNF　matrix　as　water　molecule　transfer　channels,　about　1.16　g　g-1　at　25　degrees　C　and　90%　relative　humidity　within　2　h.　This　elaborate　core　shell　structural　design　provides　a　new　pathway　for　efficient　solar　thermoelectricity-freshwater　cogeneration.