We outline in this combined experimental and theoretical NMR study that sign and magnitude of J(Si,H) coupling constants provide reliable indicators to evaluate the extent of the oxidative addition of Si-H bonds in hydrosilane complexes. In combination with experimental electron density studies and MO analyses a simple structure-property relationship emerges: positive J(Si,H) coupling constants are observed in cases where M → L π-back-donation (M = transition metal; L = hydrosilane ligand) dominates. The corresponding complexes are located close to the terminus of the respective oxidative addition trajectory. In contrast negative J(Si,H) values signal the predominance of significant covalent Si-H interactions and the according complexes reside at an earlier stage of the oxidative addition reaction pathway. Hence, in nonclassical hydrosilane complexes such as Cp2Ti(PMe3)(HSiMe3-nCln) (with n = 1-3) the sign of J(Si,H) changes from minus to plus with increasing number of chloro substituents n and maps the rising degree of oxidative addition. Accordingly, the sign and magnitude of J(Si,H) coupling constants can be employed to identify and characterize nonclassical hydrosilane species also in solution. These NMR studies might therefore help to reveal the salient control parameters of the Si-H bond activation process in transition-metal hydrosilane complexes which represent key intermediates for numerous metal-catalyzed Si-H bond activation processes. Furthermore, experimental high-resolution and high-pressure X-ray diffraction studies were undertaken to explore the close relationship between the topology of the electron density displayed by the η2(Si-H)M units and their respective J(Si,H) couplings.