The sequential construction of diversified multifunctionalized thiazole derivatives through Pd-catalyzed regioselective C–H alkenylation has been accomplished. This versatile approach provides the diversified thiazole derivatives featuring orthogonal substitution patterns at the C-2, C-4 and C-5 positions from mono-substituted (2- or 4-substituted) thiazole derivatives or even more challenging simple thiazole.