Polyoxometalates are clusters of metal-oxide units, comprising a large diversity of nanoscale structures, and have many common building blocks; in fact polyoxometalate clusters are perhaps the largest non-biologically derived molecules structurally characterised. Not only can polyoxometalates have gigantic nanoscale molecular structures, but they also a have a vast array of physical properties, many of which can be specifically ‘engineered-in’. Here we describe how building block libraries of polyoxometalates can be used to construct systems with important catalytic, electronic, and structural properties. We also show that it is possible to construct complex chemical systems based upon polyoxometalates, manipulating the templating/self templating rules to exhibit emergent processes from the molecular to the macroscopic scale.