Single crystals of α-Cu5O2(SeO3)2Cl2 are successfully prepared by the chemical vapor transport method, and their structural, magnetic, thermal, and dielectric properties are investigated as a function of temperature and magnetic field. Magnetization and specific heat measurements indicate a long-range antiferromagnetic transition at TN = 32 K. The spin ordering with a propagation vector q = (1/2 0 0) below TN is determined from the neutron diffraction patterns. The dielectric data reveal an anomaly near TN. Magnetic field-dependent dielectric measurements below TN = 32 K suggest a notable magnetodielectric effect with the scaling of magnetodielectric ∝ M2. Additionally, two more dielectric and associated specific heat anomalies are noticed above TN, collaborating with the synchrotron x-ray diffraction studies. These studies provide evidence that the bow-tie lattice of α-Cu5O2(SeO3)2Cl2 is a new magnetoelectric material.