Ultra-high throughput systems and methods are used for sampling large numbers of different materials from surfaces of substantially planar library storage components. The systems and methods typically employ: microfluidic devices having integrated capillary elements for carrying out the analysis of the sampled materials; library storage components, e.g., planar solid substrates, capable of retaining thousands, tens of thousands and hundreds of thousands of different materials in small areas; sensing systems for allowing rapid and accurate sampling of the materials by the microfluidic devices, and associated instrumentation for control and analysis of the overall operation of these systems.