Palladium-catalyzed dearomative [2+2+1] annulations of aryl ethers with alkynes are reported via para-selective C–H functionalization, providing highly functionalized spirocyclohexadienones in moderate to excellent yields under mild reaction conditions. Importantly, mechanistic investigation indicated an unusual C–O bond cleavage was involved. Moreover, polyarylated naphthalenes could be obtained via oxidative [2+2+2] annulation by tuning aryl ethers from monomethoxybenzenes to polymethoxybenzenes under an identical catalytic system.