A direct and regioselective C1-acyloxylation of indolizines was developed via palladium-catalyzed C-H functionalization. A series of indolizines were successfully acyloxylated at the C1 position with the tolerance of a broad range of functional groups. In this reaction, high regioselectivity was achieved in the absence of a directing group. This work represents the first example of indolizine acyloxylation via C-H activation.