Nanolamellar MAX phase compounds (Cr0.5V0.5)n+1AlCn are formed with n = 1, 2 and 3, and their 300 K structure is studied in detail by high-resolution neutron diffraction. While the n = 1 compound is found to have complete disordering of vanadium and chromium in the metallic layers, the n = 2 and 3 compounds show strong tendency for these elements’ ordering, with the layer in the 2a(0,0,0) site of (Cr0.5V0.5)3AlC2 fully occupied by vanadium. The thermal expansion dependency of temperature is also studied by neutron diffraction for 2 < T < 550 K, revealing a negligible thermal expansion below 100 K for all of the compounds.