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This paper deals with the design of a robust sliding mode‐based extremum‐seeking controller aimed at the online optimization of a class of uncertain reaction systems. The design methodology is based on an input–output linearizing method with variable‐structure feedback, such that the closed‐loop system converges to a neighborhood of the optimal set point with sliding mode motion. In contrast with previous extremum‐seeking control algorithms, the control scheme includes a dynamic modelling‐error estimator to compensate for unknown terms related with model uncertainties and unmeasured disturbances. The proposed online optimization scheme does not make use of a dither signal or a gradient‐based optimization algorithm. Practical stabilizability for the closed‐loop system around to the unknown optimal set point is analyzed. Numerical experiments for two nonlinear processes illustrate the effectiveness …