The aim of the present study was to identify the effect of solute Ni element on the plastic deformation and its thermal activation process of 18Cr ferritic stainless steels. Single-crystal micropillars with different diameters of approximately 2 and 5 μm were fabricated on the surface of Fe–18%Cr–Ni alloy sheets containing different contents of Ni (0–2 mass%). Compression tests were performed on the micropillars at different initial strain rates to investigate the strain rate sensitivity (m) of stress for the slip initiation and the specimen-size dependence of the m value. In micropillars with a small diameter of 2 μm, the Fe–18%Cr binary alloy specimen exhibited a relatively higher strain-rate sensitivity of initial slip stress (m = 0.12), whereas m was reduced to 0.01 by adding 2% Ni. The same trend was observed in micropillars with a larger size of approximately 5 μm. The experimental results were utilized to evaluate the activation volume of plastic deformation. The activation volumes of the Fe–18%Cr alloy and alloy containing 1% Ni followed the specimen-size dependence trend of activation volume in bcc metals; however, the alloy containing 2% Ni exhibited larger activation volumes, suggesting a different thermal activation process presumably due to the significant interaction that occurred between dislocations and solute Ni atoms in bcc solid-solutions.