There are currently many well-established applications for recycled rubber from end-of-life tires (ELT), but it is essential to investigate and seek new approaches to enhance the value of these products. Recent developments in new technologies and innovative recycling and devulcanization processes have opened up new perspectives for ELT crumb rubber. To promote the use of these products in newly added value applications, it is essential to develop and optimize methods that allow the characterization of parameters related to the ultimate properties of potential final applications. In this respect, a novel characterization methodology based on advanced 1H double-quantum (DQ) nuclear magnetic resonance experiments has been applied for the first time to quantify the key parameters that characterize the structure of ELT crumb rubber after diverse recycling processes: from simple mechanical grinding to complex devulcanization methods. This experimental approach enables the quantification of parameters that define the network structure of rubber, such as the nonelastic network defects (sol fraction, dangling chain ends, loops), the cross-link density, and the heterogeneity of the network, directly from rubber granulate and powder (without any additional sample preparation steps), overcoming most of the drawbacks and uncertainties that limit the application of traditional rubber characterization methods (e.g., equilibrium swelling experiments). By applying this experimental approach, it is possible to identify and quantify the actual technical limits for a complete selective devulcanization process of ELT crumb rubber.