1H and 13C NMR chemical shifts and IR SCN stretching frequencies for 3- and 3,5-substituted thiocyanatobenzenes have been measured at high dilution in an inert solvent. Substituent effects are additive for δC of the SCN group, δH and vSCN in the two series, but not for the ring δC. Most data sets gave excellent correlations ( r > 0.99) with substituent effects using single, dual and triple parameter approaches. The SCN carbon experiences a reverse substituent effect through both polar and resonance pathways of the electronic effect of the substituent(s), with σ F accounting for 96% of it. In contrast, vSCN shows a normal substituent effect through both pathways, with σ F accounting for 92% of it. δC-1, under the influence of the ipso SCN, shows complete dependency on σ F while δC-6 ( ortho SCN) shows a low ϱ F value; the other carbon shifts show typical ϱ F and ϱ R values. All δH show a normal substituent effect through both pathways.