EPR spectra of V4+ in zirconolite-rich ceramics with nominal composition Ca1.00Gd0.01Zr0.99Ti1.99V0.01O7.00 were studied. It was found that these spectra contain the lines of Gd3+ and V4+ ions. Computer calculation of the spectrum of V4+ with hyperfine structure showed that it is a superposition of two spectra of V4+ ions due to V4+ ions substituting for Ti4+ ions in two non-equivalent positions of these ions in zirconolite lattice. The analysis of linewidths of hyperfine components of the V4+ spectrum indicates the correlated positions of Gd and V in the zirconolite lattice with the distance between them r(v)-Gd similar to1 nm. It is assumed that V5+ ions also substitute for Ti4+ ions and compensate the electric charge of Gd3+ ions, which replace Zr4+ in the same unit cell of zirconolite crystal lattice.