In this work we develop a variational relativistic density matrix renormalization group (DMRG) approach within the exact-two-component (X2C) framework (X2C-DMRG), using spinor orbitals optimized with the two-component relativistic complete active space self-consistent field. We investigate fine-structure splittings of p- (Ga, In, Tl) and d-block (Sc, Y, La) atoms and excitation energies of monohydride molecules (GeH, SnH, and TlH) with X2C-DMRG calculations using an all-electron relativistic Hamiltonian in a Kramers-unrestricted basis. We find that X2C-DMRG yields accurate 2P and 2D splittings compared to multireference configuration interaction with singles and doubles (MRCISD). We also investigated the degree of symmetry breaking in the atomic multiplets and convergence of electron correlation in the total energies. Symmetry breaking can be large in some cases (∼30 meV); however, increasing the number of renormalized block states m for the DMRG optimization recovers the symmetry breaking by several orders of magnitude. Encouragingly, we find the convergence of electron correlation to be close to MRCISDTQ5 quality. Relativistic X2C-DMRG approaches are important for cases where spin-orbit coupling is significant and the underlying reference wave function requires a large determinantal space. We are able to obtain quantitatively correct fine-structure splittings for systems up to 1019 number of determinants with traditional CI approaches, which are currently unfeasible to converge for the field.