The first solids that form as a cooling white dwarf (WD) starts to crystallize are expected to be greatly enriched in actinides. This is because the melting points of WD matter scale as Z^{5/3} and actinides have the largest charge Z. We estimate that the solids may be so enriched in actinides that they could support a fission chain reaction. This reaction could ignite carbon burning and lead to the explosion of an isolated WD in a thermonuclear supernova (SN Ia). Our mechanism could potentially explain SN Ia with sub-Chandrasekhar ejecta masses and short delay times.