There is provided a hard-to-sinter constraining green sheet and a method of manufacturing a multilayer ceramic substrate using the same. The hard-to-sinter constraining green sheet disposed at least one of top and bottom surfaces of a non-sintered multi-layer ceramic substrate, the hard-to-sinter constraining green sheet including: a first constraining layer having a surface to be positioned on the multi-layer ceramic substrate, the first constraining layer including a first organic binder and a first inorganic powder having a spherical shape or a quasi-spherical shape; and a second constraining layer bonded to a top surface of the first constraining layer and including a second organic binder and a second inorganic powder having a flake shape, the second constraining layer having a powder packing density lower than that of the first constraining layer.