We report a simple, rapid, and solvent-free methodol. for solid-state polymns. yielding poly(phenylene vinylenes) (PPVs) promoted by ball-milling. This solid-state Gilch polymn. method produces PPVs in as little as five minutes of milling. Detailed investigations of the parameter space governing the solid-state polymn., i.e., milling time, base strength, solid-state diln., milling frequency, and size of milling balls, revealed that polymn. by ball-milling is a rapid process achieving mol. no. av. wts. of up to 40 kDa in up to 70% yield. To explore the scope, a solid-state polymn. via the dithiocarbamate precursor route is explored. [on SciFinder(R)]