Ligand-to-metal charge transfer (LMCT) excitation has emerged as a potent strategy for the selective generation of heteroatom-centered radicals, yet its full potential in modulating open-shell radical pathways remains underexplored. Here, we present a photocatalytic methylative cross-coupling reaction that capitalizes on the synergistic interplay between LMCT and Ni catalysis, enabling the use of -butanol as an efficient and benign methylating reagent. The electron-deficient ligand 2,6-ditrifluoromethyl benzoate facilitates Ce(IV)-mediated bond scission of -butanol, generating a methyl radical that is subsequently captured by the Ni catalytic cycle to form C-CH bonds. Under mild reaction conditions, this strategy affords efficient methylation of sp carbons adjacent to carbonyls and sp centers, demonstrating broad functional group tolerance and applicability in late-stage functionalization of bioactive molecules. Additionally, trideuteromethylative coupling can be facilely achieved using commercial -butanol-. This approach circumvents the need for traditional -butoxy radical precursors, such as peroxides, while strategically modulating the radical pathway to favor β-scission and suppress unwanted -butoxy radical formation in solution. Mechanistic studies reveal that the benzoate ligand plays a crucial role in enabling LMCT excitation and facilitating methyl radical generation, supporting a concerted Ce-OR and β-C-C bond homolysis mechanism, further evidenced by the modulation of regioselectivity in alkoxy radical-mediated β-scission.