Relativistic free-motion time-of-arrival theory for massive spin-1/2 particles is systematically developed. Contrary to the nonrelativistic time-of-arrival operator studied thoroughly in previous literatures, the relativistic time-of-arrival operator possesses self-adjoint extensions because of the particle-antiparticle symmetry. The nonrelativistic limit of our theory is in agreement with the nonrelativistic time-of-arrival theory. By comparing the time-of-arrival operator with the Hamiltonian operator of a free Dirac particle, one can show a duality between position space and momentum space.