The platinum complex [Pt(ItBuiPr′)(ItBuiPr)][BArF] interacts with tertiary silanes to form stable (<0 °C) mononuclear PtII σ‐SiH complexes [Pt(ItBuiPr′)(ItBuiPr)(η1‐HSiR3)][BArF]. These compounds have been fully characterized, including X‐ray diffraction methods, as the first examples for platinum. DFT calculations (including electronic topological analysis) support the interpretation of the coordination as an unusual η1‐SiH. However, the energies required for achieving a η2‐SiH mode are rather low, and is consistent with the propensity of these derivatives to undergo Si−H cleavage leading to the more stable silyl species [Pt(SiR3)(ItBuiPr)2][BArF] at room temperature.