The solid molecular complexes formed betvveen substituted acetanilides and trinit- robenzenes are prepared and investigated by element analysis, IR and lH NMR spectroscopy. The results of element analysis confirm the formation of 1:1 complexes in a püre State. The spectral changes reveal that picric acid forms complexes with TT-K*, n-rc* electronic interac- tions and proton transfer while picrylchloride and trinitrobenzene result their complexes through K — K* and n - K* transitions. The results are confirmed bv NMR