It was found that in double MgO based perpendicular magnetic tunneling junction spin-valves ex-situ annealed at 400 °C, the tunneling magnetoresistance ratio was extremely sensitive to the material and thickness of the nanoscale spacer: it peaked at a specific thickness (0.40~0.53 nm), and the TMR ratio for W spacers (~134%) was higher than that for Ta spacers (~98%). This dependency on the spacer material and thickness was associated with the (100) body-centered-cubic crystallinity of the MgO layers: the strain enhanced diffusion length in the MgO layers of W atoms (~1.40 nm) was much shorter than that of Ta atoms (~2.85 nm) and the shorter diffusion length led to the MgO layers having better (100) body-centered-cubic crystallinity.