In roll-to-roll (R2R) processing, uniformity of the web is a crucial factor that can guarantee high coating quality. To understand web defects due to thermal deformation, we analyzed the effects of web unevenness on the coating quality of an yttria-stabilized zirconia (YSZ) layer, a brittle electrolyte of solid oxide fuel cells (SOFCs). We used finite element analysis to analyze the thermal and mechanical deformations at different drying temperatures. A YSZ layer was also coated using R2R slot-die coating to observe effects of web unevenness on the coating quality. It was seen that web unevenness was generated by thermal deformation due the conduction and convection heat from the dryer. Owing to varying web unevenness with time, the YSZ layer developed cracks. At higher drying temperatures, more coating defects having larger widths were generated. Results indicated that web unevenness at the coating section led to coating defects, which could damage the SOFC and decrease its yield in the R2R process. From this study, we suggest that coating defects, generated by the web unevenness owing to the convection and conduction heat, should be considered for the high-volume production of brittle electrolytes using the R2R process.