This paper studies the mean square exponential synchronization control of the Markovian jump chaotic Lur'e systems (MJCLSs) with multiple time delays via aperiodic sampling. Firstly, by introducing the mode-dependent single/double integral terms and considering the system state at the sampling instant, a new mode-dependent Lyapunov functional based on the looped-functional is constructed. On the basis of the constructed functional and by estimating the expectation of the solution of MJCLSs with multiple time delays, an exponential synchronization criterion in the mean square sense is presented. Then, based on the obtained stability conditions, a design method for aperiodic sampled-data controller (ASDC) to ensure the exponential synchronization is proposed. Finally, the effectiveness of the developed method is demonstrated by the Chua’s circuit model and a neural network model. Compared with the existing literature, an admissible larger upper bound of sampling period can be obtained.