This work investigates the use of MRI radio-frequency (RF) pulses designed within the framework of optimal control theory for image contrast optimization. The magnetization evolution is modeled with Bloch equations, which defines a dynamic system that can be controlled via the application of the Pontryagin Maximum Principle (PMP). This framework allows the computation of optimal RF pulses that bring the magnetization to a given state to obtain the desired contrast after acquisition. Creating contrast through the optimal manipulation of Bloch equations is a new way of handling contrast in MRI, which can explore the theoretical limits of the system.Simulation experiments carried out on-resonance quantify the contrast improvement when compared to standard T1T1 or T2T2 weighting strategies. The use of optimal pulses is also validated for the first time in both in vitro and in vivo experiments on a small-animal 4.7 T MR system. Results demonstrate their robustness to static field inhomogeneities as well as the fact that they can be embedded in standard imaging sequences without affecting standard parameters such as slice selection or echo type. In vivo results on rat and mouse brains illustrate the ability of optimal contrast pulses to create non-trivial contrasts on well-studied structures (white matter versus gray matter).