<p>The surface characteristics of a mineral is very significant in a heterogeneous system. We have investigated the structural, electronic characteristics of fluorite(CaF₂) {111} surface with different termination through the density functional theory(DFT) calculation. We compared the calculated lattice parameters of fluorite with reported data and chose the reasonable functional and approximation method for the sequent calculation. We constructed and relaxed fluorite {111} surface with 3 terminations: (i) the termination with 4 exposed calcium atoms(Ca₄-termination), (ii) one with 4 calcium atoms and one fluorine atom(Ca₄F-termination), and (iii) one with 4 fluorine atoms (F₄-termination). The results show that the density of broken bonds on Ca₄F-termination is the smallest. The relaxation degrees show the rank of Ca₄F &lt; Ca₄ &lt; F₄. The Ca₄F-termination has the smallest surface energy. The Mulliken charge population and density of state(DOS) of these terminations also show that the electron state of Ca₄F-termination is relatively similar to that of the bulk and this is the safest. This investigation on various terminations offers a new understanding on characteristics of fluorite {111} surface and provides the useful information for the incoming study such as surface reactivity and dissolubility of fluorite.</p>