Cationic amidotitanocene complexes [Cp2Ti(NPhAr)][B(C6F5)4] (Cp=η5‐C5H5; Ar=phenyl (1 a), p‐tolyl (1 b), p‐anisyl (1 c)) were isolated. The bonding situation was studied by DFT (Density Functional Theory) using EDA‐NOCV (Energy Decomposition Analysis with Natural Orbitals for Chemical Valence). The polar Ti−N bond in 1 a–c features an unusual inversion of σ and π bond strengths responsible for the balance between stability and reactivity in these coordinatively unsaturated species. In solution, 1 a–c undergo photolytic Ti−N cleavage to release Ti(III) species and aminyl radicals ⋅NPhAr. Reaction of 1 b with H3BNHMe2 results in fast homolytic Ti−N cleavage to give [Cp2Ti(H3BNHMe2)][B(C6F5)4] (3). 1 a–c are highly active precatalysts in olefin hydrogenation and silanes/amines cross‐dehydrogenative coupling, whilst 3 efficiently catalyzes amine‐borane dehydrogenation. The mechanism of olefin hydrogenation was studied by DFT and the cooperative H2 activation key step was disclosed using the Activation Strain Model (ASM).