Li-metal batteries show remarkable potential for achieving high energy densities; however, their practical application is hindered by Li dendrite growth and significant volume changes during cycling. The present study was aimed at resolving these issues by creating a novel functionalized MXene scaffold (β-PM) for anode-less Li metal batteries, designed to suppress dendrite formation and improve the cycling stability. The β-PM scaffold integrates fluorine-aligned polyvinylidene fluoride on its surfaces, which expands the interlayer spacing and provides abundant F-rich sites. This unique architecture promotes efficient Li-ion diffusion, resulting in unusual bead-shaped Li deposits while effectively preventing dendrite formation and providing favorable accommodation sites for Li storage. Consequently, the β-PM scaffold contributes to significantly improved the cycling stability and electrochemical performance, establishing it as a promising platform for advanced, dendrite-free energy storage applications.