Tri-α-naphthylbenzene (TαNB) can exist as either a crystalline or glassy solid at ambient temperatures, making it a unique matrix in matrix-assisted laser desorption/ionization (MALDI) spectroscopy. Electrosprayed TαNB is crystalline and has a melting point of 180 ± 2 °C, as measured by differential scanning calorimetry (DSC). A glass of TαNB is obtained upon heating above the crystalline melting point with a glass transition temperature of 68 ± 2 °C having no remaining crystallinity. MALDI samples containing mass fraction 1% polystyrene (PS) are run in both the crystalline and amorphous states. In the crystalline state, there is a strong spectrum typical of PS, but upon melting and quenching to the glassy state, the MALDI signal disappears. If the transparent, amorphous sample is treated with 1-butanol, it becomes white, and the MALDI signal returns. DSC shows that the 1-butanol treatment leads to the return of some of the crystallinity. Small angle neutron scattering (SANS) shows that the crystalline state has large aggregations of PS while the amorphous state has molecularly dispersed PS molecules. MALDI gives strong signals only when there are large aggregations of polymer molecules, with individually dispersed molecules producing no signal. Published in 2002 by John Wiley & Sons, Ltd.