In the Li2CaSiO4 crystal, in addition to intense axial centers of Cr4+, the EPR spectra of impurity ions Mn2+ (S = 5/2), Gd3+ (S = 7/2), and Cu2+ (S = 1/2) have been discovered and studied. Manganese and gadolinium ions exhibit spectra of tetragonal symmetry, copper ions are represented by spectra of both axial and triclinic symmetry. The parameters of the spin Hamiltonians of tetragonal centers are determined. It was shown that Mn2+ and Gd3+ ions substitute for calcium ions with an eightfold oxygen environment, copper ions are localized in lithium positions with a tetrahedral environment. The reasons for the appearance of Cu2+ triclinic centers are discussed.