Slime mold algorithm (SMA) is a nature-inspired algorithm that simulates the biological optimization mechanisms and has achieved great results in various complex stochastic optimization problems. Owing to the simulated biological search principle of slime mold, SMA has a unique advantage in global optimization problem. However, it still suffers from issues of missing the optimal solution or collapsing to local optimum when facing complicated problems. To conquer these drawbacks, we consider adding a novel multi-chaotic local operator to the bio-shock feedback mechanism of SMA to compensate for the lack of exploration of the local solution space with the help of the perturbation nature of the chaotic operator. Based on this, we propose an improved algorithm, namely MCSMA, by investigating how to improve the probabilistic selection of chaotic operators based on the maximum Lyapunov exponent (MLE), an inherent property of chaotic maps. We implement the comparison between MCSMA with other state-of-the-art methods on IEEE Congress on Evolution Computation (CEC) i.e., CEC2017 benchmark test suits and CEC2011 practical problems to demonstrate its potency and perform dendritic neuron model training to test the robustness of MCSMA on classification problems. Finally, the parameters’ sensitivities of MCSMA, the utilization of the solution space, and the effectiveness of the MLE are adequately discussed.