Abstract: We establish a setting - atoms in optical superlattices with period 2 - in which one can experimentally probe signatures of the process of local relaxation and apparent thermalization in non-equilibrium dynamics without the need of addressing single sites. This opens up a way to explore the convergence of subsystems to maximum entropy states in quenched quantum many-body systems with present technology. Remarkably, the emergence of thermal states does not follow from a coupling to an environment, but is a result of the complex non-equilibrium dynamics in closed systems. We explore ways of measuring the relevant signatures of thermalization in this analogue quantum simulation of a relaxation process, exploiting the possibilities offered by optical superlattices.