Abstract: EPR spectra of impurity ions of Mn2+ (S = 5/2), Gd3+ (S = 7/2), and Cu2+ (S = 1/2) were found and investigated in addition to the intensive signals of axial centers of Cr4+ in the Li2CaSiO4 crystal. Manganese and gadolinium ions show spectra of tetragonal symmetry; copper ions show both spectra of axial and triclinic symmetry. Parameters of the spin Hamiltonians for the tetragonal centers were determined. Ions of Mn2+ and Gd3+ were shown to replace calcium ions with octahedral oxygen environment; copper ions are localized on lithium positions having tetrahedral environment. The reasons for appearing of triclinic Cu2+ centers are discussed.