A 4-hydroxyacetophenone oxime-derived palladacycle catalyzes the Mizoroki–Heck reaction of allyl alcohols with aryl iodides, bromides, and chlorides in aqueous and organic solvents. The reaction takes place in the presence of dicyclohexylmethylamine or cesium carbonate as bases, the addition of tetrabutylammonium bromide (TBAB) as additive for aryl bromides and chlorides being necessary. Under these reaction conditions, β-arylated aldehydes and ketones are mainly obtained using a rather low loading of palladium (0.1–1 mol %). Similar catalytic activity is shown by a Kaiser oxime resin-derived palladacycle, which allows one to perform recycling and reusing experiments with low Pd leaching. The high regio- and chemoselectivity observed supported that these palladacycles, working as a source of Pd(0) species, operates mainly through a neutral mechanism. This methodology has been applied to the synthesis of important β-arylated carbonyl compounds, such as 4-phenylbutan-2-one, 4-(4-hydroxyphenyl)butan-2-one, dihydrochalcones, the anti-inflamatory nabumetone, and the fragance β-lilial®. γ-Arylation is observed in the reactions of allyl alcohol and but-3-en-2-ol with 2-iodoaniline giving mainly the corresponding quinolines. The same tendency is observed in the case of 1,1-dimethylallyl alcohol affording either γ-arylated alcohols or (E)-1-arylisoprenes.