Six different salts of the weakly coordinating anion [Al(OTeF₅)₄]⁻were synthesized and characterized spectroscopically. The alkali and silver salts M[Al(OTeF₅)₄] (M = Ag, Li, Na, K, Rb) were obtained by a protonation reaction involving the Brønsted acid H[Al(OTeF₅)₄](solv). In the case of the lithium and silver salt, crystals of the solvent‐coordinated [Li(thf)₄][Al(OTeF₅)₄(thf)₂] and [Ag(thf)₆][Al(OTeF₅)₄(thf)₂] were characterized by low‐temperature X‐ray diffraction, revealing a sixfold coordinated central aluminum atom. By a metathesis reaction, the oxidizing nitrosonium salt [NO][Al(OTeF₅)₄] was obtained and its reactivity was demonstrated by a reaction with white phosphorus. By low‐temperature NMR spectroscopy the selective formation of [NOP₄]⁺ species was confirmed. All of the prepared salts represent useful starting materials for the further introduction of the weakly coordinating anion [Al(OTeF₅)₄]⁻ into a given system.