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Several multiple model adaptive control architectures have been proposed in the literature. Despite many advances in theory, the crucial question of how to synthesize the pairs model/controller in a structurally optimal way is to a large extent not addressed. In particular, it is not clear how to place the pairs model/controller is such a way that the properties of the switching algorithm (e.g., number of switches, learning transient, final performance) are optimal with respect to some criteria. In this work, we focus on the so-called multi-model unfalsified adaptive supervisory switching control (MUASSC) scheme; we define a suitable structural optimality criterion and develop algorithms for synthesizing the pairs model/controller in such a way that they are optimal with respect to the structural optimality criterion we defined. The peculiarity of the proposed optimality criterion and algorithms is that the optimization is carried out so as to optimize the entire behavior of the adaptive algorithm, i.e., both the learning transient and the steady-state response. A comparison is made with respect to the model distribution of the robust multiple model adaptive control (RMMAC), where the optimization considers only the steady-state ideal response and neglects any learning transient.