The substrate with a multilayer reflective film includes a substrate and the multilayer reflective film configured to reflect exposure light, the multilayer reflective film comprising a stack of alternating layers on a substrate, the alternating layers including a low refractive index layer and a high refractive index layer, in which the multilayer reflective film contains molybdenum (Mo) and at least one additive element selected from nitrogen (N), boron (B), carbon (C), zirconium (Zr), oxygen (O), hydrogen (H) and deuterium (D), and the crystallite size of the multilayer reflective film calculated from a diffraction peak of Mo (110) by X-ray diffraction is 2.5 nm or less.