Members of the solid solution series of CeRu1-xNixAl can be obtained directly by arc melting of the elements, The presented compounds with 0.1 <= x <= 0.85 crystallize in the orthorhombic space group Pnma (No. 62) in the LaNiAl structure type, while for 0.9 <= x <= 1; the hexagonal ZrNiAl-type structure is found. The orthorhombic members exhibit an anomaly in the trend of the lattice parameters as well as an interesting behavior of the magnetic susceptibility, suggesting that the cerium cations exhibit no local moment. Besides the mixed-valent nature of the cerium cations, valence fluctuations along with a change in the cerium oxidation state depending on the nickel content have been found. The oxidation state has been determined from the magnetic data and additionally by XANES. Density functional theory calculations have identified the shortest Ce-Ru interaction as decisive for the stability of the orthorhombic solid solution.