The present paper focuses on the direct synthesis of NiGa layered double hydroxides (LDHs) by concomitant addition of Ni and Ga chloride in solution with NaOH solution, at a constant pH value of 6.5. Various Ni/Ga ratios (Ni/Ga = 2, Ni/Ga = 4, or Ni/Ga = 6) were investigated, and samples were collected after successive additions. Each sample was then analyzed by small-angle X-ray scattering (SAXS) to derive information about the shape of the objects formed upon synthesis. In parallel Ni K-edge and Ga K-edge extended X-ray absorption fine structure (EXAFS) analysis were carried out on relevant samples to obtain information on the local structure of the species in suspension. SAXS curves reveal significant changes. At the beginning of the synthesis, for low added volumes (V(s)), the suspension appears to contain both monodimensional and bidimensional objects. For higher V(s), the monodimensional objects disappear and only platelike particles are detected in the suspension. EXAFS results show that all the added gallium atoms are involved in a solid Ni-Ga LDH phase throughout the whole synthesis. In contrast, some nickel cations do not precipitate in the Ni-Ga LDH. At the beginning of the synthesis, for low added volumes they are also involved in the formation of fibrous polycations. For higher added volumes, the fibers are not observed anymore and monomeric nickel species are then present in the suspension.