Herein, we have demonstrated the application of bench-stable polyfluorinated alcohols as fluoroalkylating reagents for a sequential one-pot transformation with ketones to R-CF2-embedded 1,5-diketones and pyridines enabled by a nickel catalyst. The protocol is tolerant to a range of functional groups (>31 examples and up to 85% yield) and perfluoro alcohols and releases H2 and H2O as byproducts. Preliminary mechanistic studies, EPR analyses, and deuterium scrambling experiments were performed, and observed PC-H/PC-D = 2.12.