A new europium silicate, NaEuSi3O7(OH)2 (denoted as 1), was synthesized under high-temperature and high-pressure conditions, and structurally characterized by single-crystal and powder X-ray diffraction (XRD) analyses. The single-crystal XRD analysis of 1 revealed that its structure was based on SiO4 tetrahedron single chains, which were connected together by the EuO6 polyhedron via vertex oxygen atoms forming a three-dimensional framework of 1. It contained 4, 6-ring channels along the [010] direction, which were delimited by the SiO4 tetrahedron and EuO6 polyhedron. The Na(+) ions were located in the 6-ring channels along the [010] direction to achieve the charge balance. The luminescence properties of 1 were also investigated.