The enantioselective allylic alkylation of nitro ketene aminals with racemic allylic alcohols was realized by iridium/acid dual catalysis. An allyl group was installed on the α-position of nitro ketene aminals in a branched-selective manner in high efficiency with excellent enantioselectivities (93-99% ee). The protocol was applied to the late-stage modification of neonicotinoid insecticides, which directly furnished a novel neonicotinoid analogue with good insecticidal activity against Aphis craccivora (LC50 = 6.40 mg/L). On the basis of the control experiment, an aza-ene-type allylic alkylation reaction mechanism was proposed.