The platinum(II) complex [PtCl2(COD)] (2; COD = 1,5‐cyclooctadiene) reacted with 1 and 2 equiv. of 2‐(diphenylphosphanyl)benzaldehyde oxime (1) to generate [PtCl2{κ2‐(P,N)‐2‐Ph2PC6H4CH=NOH}] (3) and [Pt{κ2‐(P,N)‐2‐Ph2PC6H4CH=NOH}2][Cl]2 (4), respectively. Deprotonation of the oxime hydroxyl group of 3 with Na2CO3 led to the selective formation of the dinuclear species (µ‐O)‐[PtCl{κ2‐(P,N)‐2‐Ph2PC6H4CH=NO}]2 (5), while the related methylated derivative (µ‐O)‐[PtMe{κ2‐(P,N)‐2‐Ph2PC6H4CH=NO}]2 (7) could be obtained from the direct reaction of [PtMe2(COD)] (6) with the phosphino‐oxime ligand 1. In the case of 4, its treatment with Na2CO3 yielded complex [Pt({κ2‐(P,N)‐2‐Ph2PC6H4CH=NO}2H)][Cl] (8), as a result of the deprotonation of only one of the OH groups of 4. On the other hand, contrary to what was observed with 6, no deprotonation of the oxime occurred in the reaction of [PtMe3I]4 (9) with 1, from which the mononuclear PtIV derivative fac‐[PtIMe3{κ2‐(P,N)‐2‐Ph2PC6H4CH=NOH}] (10) was isolated. The solid‐state structures of compounds 3, 4, 7 and 10 were determined by X‐ray crystallography. In addition, the potential of all the synthesized complexes as catalysts for the dehydrogenative coupling of hydrosilanes with alcohols is also briefly discussed.