A multivariable adaptive decoupling control scheme is proposed based on stochastic configuration networks with serial-parallel switching distribution (SPSCN). Firstly, a linear controller is designed by combining a PID controller, feedback decoupling, and one-step optimal control. Secondly, a nonlinear controller is presented to deal with higher-order nonlinear terms and unknown external perturbations. SPSCN is used to improve the prediction accuracy of unmodeled dynamics. It combines uniform and normal search strategies in a serial-parallel fashion, aiming at improving the node quality and reducing the model complexity. The approximation performance of the SPSCN algorithm is demonstrated by performing approximation experiments with two functions and four benchmark datasets. Compared with the generalized minimum variance control (GMVC) algorithm in controlling the process of cement raw material decomposition, our proposed control scheme outperforms.