Two new selenite compounds Ca₂Ni(HSeO₃)₂(SeO₃)₂ (CaNi) and Na₂Cu(SeO₃)₂·2H₂O (NaCu) were obtained by a hydrothermal method. Both compounds crystallize in the triclinic system of space group P, featuring a selenite-bridged one-dimensional (1D) spin-chain structure running along the a-axis. Magnetic measurements indicate that CaNi undergoes a long-range antiferromagnetic order (LRO) at T_N = ∼3.8 K, while NaCu does not exhibit a LRO down to 2 K but the onset of a short-range correlation at T_M = ∼30 K. The intrachain exchange coupling J/k_B = −2.59 K for CaNi and J/k_B = −47.13 K for NaCu can be estimated by a fit using the 1D spin-chain model. The thermogravimetric analyses show that both compounds are stable below 130 °C. The UV–vis diffuse reflectance spectra indicate that the band gaps of CaNi and NaCu are 4.38 eV and 3.18 eV, respectively.