Gadolinium-doped ceria (GDC) is sought-after as an electrolyte layer in solid oxide fuel cells because of its high ionic conductivity and low treatment temperature. Recently, some studies have been reported to produce a component layer of solid oxide fuel cell using a Roll-to-Roll (R2R) system because of its characteristics of the cost-effective and eco-friendly advantages. However, the brittleness and low density of GDC prevent it from being mass-produced via the R2R continuous process. Therefore, we attempted to improve the density of GDC-based multi-electrolyte layers through an optimized R2R calendaring process. The finite element method was employed to determine suitable materials for the calendering rolls and the maximum calendering pressure that would reduce the thickness and porosity of the coated electrolyte layer without producing cracks in the layer. The effect of the number of calendering processes on the thickness and porosity of the electrolyte layers was examined as well. Silicon and steel were observed to be best-suited as the materials for the top and bottom rolls, respectively. Moreover, the maximum permissible calendering pressure was determined to be 15 MPa, while the ideal number of calendering processes was found to be 5. Experimental observations using scanning electron microscopy confirmed that the optimized calendering process reduced the thickness and porosity of the coated electrolyte layers by 16.99% and 7.04%, respectively. Thus, our findings suggest that large-area, high-density GDC-based multi-electrolyte layers with smooth surfaces can be produced via the R2R process, which can enable mass production of SOFCs.