In this work, the practical prescribed performance tracking issue for a class of fractional-order nonlinear multiple-input multiple-output (MIMO) systems with asymmetric full-state constraints and unmeasurable system states is investigated. A neural network (NN) nonlinear state observer is developed to estimate the unmeasurable states. Furthermore, the barrier Lyapunov functions with the settling time regulator are employed to deal with the asymmetric full-state constraint from the fractional-order MIMO system. On this ground, the prescribed performance adaptive tracking control approach is designed, assuring that all system states do not exceed the prescribed boundaries, and the tracking errors converge to the predetermined compact sets within a predefined time. Finally, two simulation examples are presented to show the effectiveness and practicability of the proposed control scheme.