Electrolyte　plays　a　dominant　role　in　solving　the　various　challenges　of　Li-metal　batteries　(LMBs).　The　complex　competition　coordination　and　diversity　of　the　anion　coordination　clusters　in　electrolytes　are　still　unclear.　In　this　paper,　an　anion-dominated　dynamic　coordination　field　(ADCF)　theory　is　proposed　to　reasonably　explain　the　coordination　behavior　in　the　high-concentration,　localized　high-concentration,　and　weak-ionization　localized　high-concentration　electrolytes,　which　is　based　on　specific　characterizations　and　theoretical　calculations.　The　novel　model　selects　the　anions　as　the　center　of　the　whole　molecular　groups/clusters,　while　the　Li+　acts　as　the　counterion　or　carrier,　which　can　promote　the　dynamic　and　elastic　movement　of　the　whole　cluster.　The　specific　coordination　clusters　could　remarkably　enhance　the　interaction　between　TFSI−　and　Li+,　and　make　the　counterion　composition　of　Li+　increase.　The　confinement　effect　of　the　coordination　field　provides　a　difficult　ionization　atmosphere　for　the　Li+,　and　enables　clusters　to　preferentially　adsorb　on　the　Li　surface,　and　construct　a　specific　solid　electrolyte　interphase　(SEI).　Furthermore,　the　electrode/electrolyte　interface　kinetics　and　the　growth　of　lithium　dendrites　are　systematically　investigated.　These　new　viewpoints　of　coordination　behavior　provide　inclusive　strategies　in　the　electrolyte　design,　and　promote　further　research　of　the　charge　transfer　or　solution　behavior.　©　2022