Functionalized arenes and arenols have diverse applications in chemical synthesis and material chemistry. Selective functionalization of arenols is a topic of prime interest. In particular, direct alkylation of arenols using alcohols is a challenging task. In this report, a ruthenium pincer catalyzed direct α-alkylation of β-naphthol using primary alcohols as alkylating reagents is reported. Notably, aryl and heteroaryl methanols and linear and branched aliphatic alcohols underwent selective alkylation reactions, in which water is the only byproduct. Notably, catalytically derived α-alkyl-β-naphthol products displayed high absorbance, emissive properties and quantum yields (up to 93.2 %). Dearomative bromination on α-alkyl-β-naphthol is demonstrated as a synthetic application. Mechanistic studies indicate that the reaction involves an aldehyde intermediate. DFT studies support this finding and further reveal that a stoichiometric amount of base is required to make the aldol condensation as well as elementary steps required for regeneration of catalytically active species. In situ-generated water molecule from the aldol condensation reaction plays an important role in the regeneration of an active catalyst. © 2023 Wiley-VCH GmbH.