A new pulse electron paramagnetic resonance method is presented to quantify the local nuclear environment of an electron spin centre. We provide a detailed assessment of this technique. We review the theoretical principles, discuss the data analysis and demonstrate an application to a spin-labelled macromolecule supported by in silico modelling. The method can be applied to the characterization of heterogeneous systems, such as unstructured or semi-structured (bio)macromolecules.