Liebig pursued a wide variety of synthetic routes for the better part of a century, but, even with Wöhler's assistance, only succeeded in producing a complex mixture with the proportions of thiocyanic acid.

In 1861, Linnemann generated appreciable quantities of thiocyanogen from a silver thiocyanate suspension in diethyl ether and excess iodine, but misidentified the minor product as sulfur iodide cyanide (ISCN).

[7] The following year, Schneider produced thiocyangen from silver thiocyanate and disulfur dichloride, but the product disproportionated to sulfur and trisulfur dicyanides.

Treating an anhydrous Pb(SCN)2 suspension in glacial acetic acid with bromine then affords a 0.1M solution of thiocyanogen that is stable for days.

[1]: 255 An alternative technique is the thermal decomposition of cupric thiocyanate at 35–80 °C:[1]: 253 In general, thiocyanogen is stored in solution, as the pure compound explodes above 20 °C[2] to a red-orange polymer.

[1]: 241  However, the sulfur atoms disproportionate in water:[1]: 241–242 [10] Thiocyanogen is a weak electrophile, attacking only highly activated (phenolic or anilinic) or polycyclic arenes.