The concept of valence-bond resonance plays a fundamental role in the theory of the chemical bond and is believed to lie at the heart of many-body quantum physical phenomena. Here we show direct experimental evidence of a time-resolved valence-bond quantum resonance with ultracold bosonic atoms in an optical lattice. By means of a superlattice structure we create a three-dimensional array of independent four-site plaquettes, which we can fully control and manipulate in parallel. Moreover, we show how small-scale plaquette resonating valence-bond (RVB) states with s- and d-wave symmetry can be created and characterized. We anticipate our findings to open the path towards the creation and analysis of many-body RVB states in ultracold atomic gases.