New 1,2,3-triazolo(thieno)stilbenes were synthesized by Wittig reaction and photochemically transformed to corresponding substituted thienobenzo/naphtho-triazoles in high isolated yields. They were prepared to study the acetyl- and butyrylcholinesterase inhibition associated with the inhibition of TNFα cytokine production and anti-inflammatory activity. The best experimental results were achieved with the allyl-thienobenzotriazole and isopropyl, p-methoxybenzyl, and hydroxybutyl substituted naphthotriazoles bearing additional chloro or methoxy groups. The allyl-thienobenzotriazole photoproduct is twice as potent an inhibitor of eqBChE compared to the standard galantamine. At the same time, this compound strongly inhibited TNFα production in PBMCs in response to the LPS stimulus. The complexes between selected compounds with the active site of BChE and AChE are assessed by docking, providing insight into the stabilizing interactions between the potential inhibitor and the active site.