Considerable attention is paid to the influence of crosslink density and crosslink structures on the behavior of polymer chains and properties of elastomers. However, a very important parameter seems to be underestimated: the modifications to the polymer chains by curatives, formed by sulfur and fragments of accelerators. We draw attention to this important contribution to performance of spatial networks. The emulsion styrene–butadiene rubber samples, cured with tetramethylthiuram disulfide and sulfur (TMTD/S8) and zinc dialkyl dithiophosphate with sulfur (ZDT/S8), were studied. They were characterized in detail in terms of crosslink density and crosslink structures. Microscale techniques were used to obtain information about the behavior of the polymer chains: positron annihilation lifetime spectroscopy (PALS) to study the free volume structure and differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) to monitor the glass transition process. Properties such as static mechanical performance and thermo-oxidative stability were also evaluated. All of the investigated characteristics were influenced by a combination of crosslink density, crosslink structures, and, to a large extent, by the modifications of the polymer chains. The effect of the modifications is dependent on the amount and the structure of the curatives' molecules. On the basis of the obtained results, the usefulness of the “phr” unit used for calculation of the curatives' amount has been queried. Furthermore, it has been demonstrated that DSC, DMA, and PALS techniques can provide evidence for the presence of the modifications on the polymer chain by curatives.