We report the synthesis of novel N-coordinated λ5-iodanes as a unique class of hypervalent iodine compounds. X-ray diffraction analysis revealed their intriguing (pseudo)cyclic structure, showcasing distinctive N⋯I-secondary bonding interactions. We demonstrate the in situ generation of reactive diacetoxy derivatives, which exhibits remarkable efficacy in alcohol oxidation reactions. Thermal stability assessments using TGA/DSC analysis provide crucial insights into the handling and potential applications of these compounds. This work expands the frontier of hypervalent iodine chemistry, offering new tools for selective oxidation reactions.