An organic chemistry experiment was devised to introduce students to the principles of solid-state and supramolecular chemistry. The experiment utilizes a template to direct the assembly of an olefin in the solid state that undergoes a [2+2] photodimerization. Although the formation of the photoproduct from 2(res)·2(4,4′-bpe) and photostability of pure 4,4′-bpe were demonstrated by comparing melting points and chromatograms, H nuclear magnetic resonance (NMR) spectroscopy was used to identify the photoproduct 4.4′-tpcb. Readily available materials were used for this organic laboratory experiment.