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The deoxygenation of 1‐alkyl‐3‐methyl‐3‐phospholene 1‐oxides, which may be regarded as trialkyl phosphine oxides (R3PO), and the reduction of dialkyl‐phenylphosphine oxides (R2PhPO) and methyl‐diphenylphosphine oxide (MePh2PO) have been elaborated by applying user‐friendly silanes, such as tetramethyldisiloxane (>SiH–O–HSi<) and polymethylhydrosiloxane ((O–SiH)n) under solvent‐free, catalyst‐free, and microwave (MW)‐assisted conditions. New silanes of type Ar2SiH2, alkyl2SiH2, and Ar3SiH were also applied in a few cases. The reactivity of the phosphine oxides and the silanes could be mapped on the basis of our experimental data.