Traditional palladium-catalyzed dearomatization of (hetero)arenes takes place via an ionic pathway and usually requires elevated temperatures to overcome the energy barrier of the dearomative insertion step. Herein, a combination of the radical and two-electron pathways is disclosed, which enables room temperature dearomative 3D transformations of nonactivated phenyl rings with Pd(0) as the catalyst. Experimental results together with density functional theory (DFT) calculations indicate a versatile pi-allyl Pd(II) species, cyclohexadienyl Pd(II), possibly is involved in the dearomatization. This species is generated by combining the cyclohexadienyl radical and Pd(I). The cyclohexadienyl Pd(II) provides chemoselective (carboamination and trieneylation), regioselective (1,2-carboamination), and diastereoselective (carbonyl-group directed face selectivity) conversions. Room temperature dearomative 3D transformations of nonactivated phenyl rings are developed possibly involving a versatile pi-allyl Pd(II) species, cyclohexadienyl Pd(II), generated by combining the cyclohexadienyl radical and Pd(I). The cyclohexadienyl Pd(II) provides chemoselective (carboamination and trieneylation), regioselective (1,2-carboamination), and diastereoselective (carbonyl-group directed face selectivity) conversions.image