Dendritic　Li　growth　is　the　root　hurdle　against　the　implementation　of　lithium　metal　anode　because　it　brings　safety　hazard,　low　columbic　efficiency　and　inferior　cycle　life.　Customized　strategies　have　been　investigated　to　achieve　uniform　lithium　deposition.　However,　little　attention　has　been　paid　to　the　fundamental　understandings　of　intrinsic　electrocrystallization,　especially　the　nucleation　behavior,　of　lithium　deposition.　In　this　work,　the　deposition　behavior　of　Li　metal　on　amorphous　substrate　and　the　difference　of　Li　electrocrystallization　among　various　crystallinities　have　been　studied　by　both　experiments　and　first-principles　calculations.　A　2D　island-like　Li　nucleation　rather　than　dispersed　submicro　grains　is　achieved　on　amorphous-AlN　modified　Cu　current　collector.　The　mechanism　underlying　the　amorphism-induced　nucleation　of　Li　metal　includes　the　enhanced　absorption　capacity　of　the　initially　deposited　Li　layer　(at　least　four　layers)　to　subsequent　Li　layers　endowed　by　amorphous　AlN　and　the　preference　to　Li　extending　rather　than　dendritic　growth　on　amorphous　AlN.　With　this　amorphism-induced　2D　island-like　nucleation,　Li　deposition　on　amorphous　AlN　exhibits　a　smooth　and　planar　morphology,　accompanied　by　the　uniformity　in　thickness.　Therefore,　both　half-cells　and　full-cells　present　enhanced　cycling　stability　and　higher　CE　using　amorphous-AlN　modified　Cu　current　collector.　©　2022