Thorough investigation of nitridophosphates has rapidly accelerated through development of new synthesis strategies. Here we used the recently developed high-pressure metathesis to prepare the first rare-earth metal nitridophosphate, Ce4Li3P18N35, with a high degree of condensation >1/2. Ce4Li3P18N33 consists of an unprecedented hexagonal framework of PN4 tetrahedra and exhibits blue luminescence peaking at 455 nm. Transmission electron microscopy (TEM) revealed two intergrown domains with slight structural and compositional variations. One domain type shows extremely weak superstructure phenomena revealed by atomic-resolution scanning TEM (STEM) and single-crystal diffraction using synchrotron radiation. The corresponding superstructure involves a modulated displacement of Ce atoms in channels of tetrahedra 6-rings. The displacement model was refined in a supercell as well as in an equivalent commensurate (3 + 2)-dimensional description in superspace group P6(3)(alpha, ss,0)0(-a - ss, a, 0)0. In the second domain type, STEM revealed disordered vacancies of the same Ce atoms that were modulated in the first domain type, leading to sum formula Ce4-0.5xLi3P18N35-1.5xO1.5x (X approximate to 0.72) of the average structure. The examination of these structural intricacies may indicate the detection limit of synchrotron diffraction and TEM. We discuss the occurrence of either Ce displacements or Ce vacancies that induce the incorporation of O as necessary stabilization of the crystal structure.