Cobalt(II) thiocyanate‐based tests are routinely used to screen cocaine products, with the formation of a blue species interpreted as a positive response. An array of other organic bases has been identified as false positives – including well‐documented cocaine product adulterant lidocaine and its salt. False positives prompt continued test development, though improvements are hindered by unresolved product structures and reaction pathways. Toward greater clarity, cobalt(II) thiocyanate reactions with cocaine hydrochloride, along with lidocaine and its salt, were investigated using multiple analytical techniques. Reactions involving cocaine hydrochloride yielded glassy, amorphous blue material while reactions of lidocaine hydrochloride monohydrate produced larger, needle‐like crystals whose structure was determined via single‐crystal X‐ray diffraction to be an ion pair (Hlidocaine+)2([Co(SCN)4]2−)·H2O. While the blue precipitate isolated from reactions involving cocaine hydrochloride was unsuitable for crystallographic structure determination, comparative ultraviolet–visible, attenuated total reflectance infrared, and Raman spectroscopic analysis – along with elemental analysis – supports that this solid is comprised of a comparable ion pair (Hcocaine+)2[Co(SCN)4]2−. Pink crystals isolated from lidocaine reaction vessels were identified as coordination compounds cis‐[CoL2(SCN)2] and trans‐[CoL2(SCN)2] where L = lidocaine, while pink crystals from both cocaine hydrochloride and lidocaine hydrochloride monohydrate reaction vessels were the coordination polymer trans‐[Co(H2O)2(SCN)2]·H2O. The results presented herein enable reaction optimization to favor a desired product, whether ion pair or coordination species.