We report the crystal structure and physical properties of two Ni5As3-based compounds RE2Ni5As3O2 (RE = Ce, Sm). The former exhibits structural phase transition from tetragonal (space group I4/mmm, 139) to orthorhombic (space group Immm, 71) symmetry at 230 K, while the latter undergoes a charge-density-wave-like structural distortion with abrupt change of Ni-As bond length. Both compounds show antiferromagnetic transitions due to RE3+ ions ordering at 4.4 and 3.4 K, accompanying with the large enhancement of Sommerfeld coefficients comparing to the nonmagnetic La analogue. Although the Cu substitution for Ni induces structural anomalies and suppression of structural transition like the behaviors in La/Pr/Nd analogues, the superconductivity is not observed in both Cu-doped RE2Ni5As3O2 (RE = Ce, Sm) above 0.25 K. Our structural refinements reveal that the lacking of superconductivity in RE2(N1-xCux)(5)As3O2 might relate to the anomalous increase of As height, h(1).