A convenient and efficient one-pot isomerization–chlorination, arylation, and etherification of several Baylis–Hillman adducts with silica chloride, an eco-friendly heterogeneous catalyst, silica chloride–arenes, and silica chloride–saturated and unsaturated alcohols as reagent systems are reported. These reactions furnished highly functionalized isomerized Baylis–Hillman derivatives in good yield. The efficiency and necessity of silica chloride catalyst was compared with thionyl chloride. A plausible mechanism of the reaction is proposed.