Syntheses of substituted pyridines and fluorinated compounds, which are often pharmaceutical targets, are important objectives in organic chemistry. Herein, we found that decarboxylative fluorination of lithium 2‐pyridylacetates occur under catalyst‐free conditions. The phenomenon can be applied to one‐pot transformation of substituted methyl 2‐pyridylacetate to 2‐(fluoroalkyl)pyridine by decarboxylative fluorination of the intermediate lithium 2‐pyridylacetate. This method was also applied to the syntheses of 2‐(difluoroalkyl)pyridines. Substituted pyridines: Decarboxylative fluorination of lithium 2‐pyridylacetates occur under catalyst‐free conditions. The phenomenon was applied to one‐pot transformation of a substituted methyl 2‐pyridylacetate into a 2‐(fluoroalkyl)pyridine. The method was also applied to the syntheses of 2‐(difluoroalkyl)pyridines (see scheme).