Nuclear magnetic resonance or NMR has been a popular non-invasive tool to study structure and dynamics of materials in fields ranging from biomedicine to petroleum engineering. The relatively lesser known low field solid state time domain NMR is now finding wider acceptance in the polymer science community as a characterization tool owing to its cost-effectiveness, simplicity and in particular to the range of information it provides. In this contribution, we highlight how this equipment, with simple as well as sophisticated measurement set-ups, can be used non-invasively to characterize the structure of elastomer materials in detail by determining the crosslink density, the distribution of crosslinks, the defect fraction and the interactions with inorganic filler. Using double quantum NMR, a method that is fast gaining acceptability, we investigated the network characteristics of photoinduced thiol-ene crosslinked elastomers. We studied the influence of selected process parameters including exposure dose and amount of crosslink chemicals on the network properties. Apart from the characterization of photochemically crosslinked elastomers, we further employed this characterization technique to study sulphur cured materials in dependence of their cure time and cure temperature. In addition to the above studies, we show here how the basic signal of NMR, the free induction decay (FID), of a semi-crystalline polymer such as poly(oxy methylene) can be successfully used to determine the morphology and can also potentially be used to study crystallization kinetics.