"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 of the proposed robust control scheme.