A novel site-specific structure-activity relationship was developed for the site-specific addition of OH radicals to (poly)alkenes at 298 K. From a detailed structure-activity analysis of some 65 known OH + alkene and diene reactions, it appears that the total rate constant for this reaction class can be closely approximated by a sum of independent partial rate constants, ki, for addition to the specific (double-bonded) C atoms that depend only on the stability type of the ensuing radical (primary, secondary, etc.), that is, on the number of substituents on the neighboring C atom in the double bond. The (nine) independent partial rate constants, ki, were derived, and the predicted rate constants (kOH,pred = Sigmak(i)) were compared with experimental k(OH,exp) values. For noncyclic (poly)alkenes, including conjugated structures, the agreement is excellent (Delta < 10%). The SAR-predicted rate constants for cyclic (poly)alkenes are in general also within <15% of the experimental value. On the basis of this SAR, it is possible to predict the site-specific rate constants for (poly)alkene + OH reactions accurately, including larger biogenic compounds such as isoprene and terpenes. An important section is devoted to the rigorous experimental validation of the SAR predictions against direct measurements of the site-specific addition contributions within the alkene, for monoalkenes as well as conjugated alkenes. The measured site specificities are within 10-15% of the SAR predictions.