Using in situ high pressure Raman spectroscopy, two structural changes were observed in a sample of the composition LiLa₅O₅(VO₄)₂. Taking this into account and by combining different conditions, three new compounds were further obtained from high pressure–high temperature synthesis. Their crystal structure description was done using the antiphase approach, which implies the presence of oxygen-centered [OLn₄] building units, where Ln is La for (1) β-LiLa₅O₅(VO₄)₂ and (2) β-LiLa₂O₂(VO₄) or Nd for (3) LiNd₅O₅(VO₄)₂ compounds. (1) crystallizes in the triclinic space group P with unit cell parameters of a = 5.8167(15) Å, b = 12.2954(28) Å, c = 18.7221(69) Å, α = 102.03(2)°, β = 98.76(2)°, and γ = 103.54(2)°; a 3D structure was deduced from the ambient pressure polymorph. (2) also crystallizes in P with a = 5.8144(7) Å, b = 5.8167(7) Å, c = 8.5272(1) Å, α = 98.184(7)°, β = 100.662(7)° and γ = 92.579(7)°. It shows a 2D structure with [La₂O₂]²⁺ layers surrounded by [LiO₄] and [VO₄] tetrahedra sharing corners and edges. (3) exhibits a 3D architecture isotypic with AP-LiLa₅O₅(VO₄)_2. The crucial role of high pressure in such types of synthesis and materials is also discussed.