Provided are a constraining green sheet and a method of manufacturing a multi-layer ceramic substrate. The constraining green sheet includes a first constraining layer and a second constraining layer. The first constraining layer has a side to be disposed on a multi-layer ceramic laminated structure and is formed of a first inorganic powder having a first particle diameter. The second constraining layer is disposed on top of the first constraining layer and is formed of a second inorganic powder having a second particle diameter larger than the first particle diameter. The second constraining layer is equal to or lower than the first constraining layer in terms of powder packing density. A shrinkage suppression rate can be increased and a de-binder passage can be secured in a firing process of the ceramic laminated structure by using the constraining green sheet formed of inorganic powders having different density and particle diameter.