The dehydrative mono-/dialkylation reactions of alcohols and β-ketoacids were realized under arylboronic acid catalysis, furnishing a series of β-aryl ketones and β-ketoesters in yields of 15-99%, with CO2 and H2O being the byproducts. In this context, the decarboxylative alkylation reaction occurred to give β-aryl ketones at 50 °C, while the decarboxylation was suppressed to generate dialkylated ester products at 0 °C. A possible catalytic cycle was proposed based on control experiments.