This paper considers the use of constrained minimum crest factor multisine signals as inputs for plant-friendly identification testing of chemical process systems. The methodology presented here effectively integrates operating restrictions, information-theoretic requirements, and state-of-the-art optimization techniques to design minimum crest factor multisine signals meeting important user-specified time and frequency domain properties. A series of optimization problem formulations relevant to problems in linear, nonlinear, and multivariable system identification are presented; these culminate with their application to the modeling of the Weischedel–McAvoy high-purity distillation column problem, a demanding nonlinear and highly interactive system. The effectiveness of these signals for modeling for control purposes and the ability to incorporate a priori nonlinear models in the signal design procedure are demonstrated in this distillation system case study.