The substituent effect (SE) is one of the most important topics in organic chemistry and related fields, and Hammett constants (σ) are commonly used to describe it. The results of the computational studies carried out for Y-R-X systems (reaction sites Y = NO2, O-; substituents X = NO2, CN, Cl, H, OH, NH2; spacers R = polyene, polyyne, acene with n = 1-5 repeatable units) show that the substituent properties depend significantly on n, the type of R, and Y. Results of the analysis of the substituent effect stabilization energy and geometrical parameters of the Y-R-X systems reveal that (i) the SE strength and its inductive and resonance components decay with the increase in spacer length, its weakening depends on the Y and R type; quantitative relations describing decay are presented; (ii) the ratio between inductive and resonance effect strength changes with n and depends on Y; (iii) differences in the substituents' properties are examples of reverse SE; (iv) in general, structural parameters are mutually well correlated as well as with the SE descriptors; (v) due to the strong O- resonance effect, the changes in π-electron delocalization within R are well correlated with the SE strength only for Y = O- systems.