The proton, affinity (PA) on the oxygen atom in silanol and siloxane derivatives is enhanced by the formation of tetrel bonds with small Lewis bases [B center dot center dot center dot R3SiOH, B center dot center dot center dot R3SiOSiR3, B center dot center dot center dot R3SiOSiR3 center dot center dot center dot B; B = H2O, CO, NH3, HCN, H2S; R = H, Me], as shown by MP2/jul-cc-pVTZ calculations. The complexed systems become more basic than ether and other carbon-related compounds, and even more basic than pyridine in some specific cases, reaching values up to 959.4 kJ/mol (H3N H3SiOSiH3 NH3 complex). Changes on PAs are directly related to very large binding energies for the protonated species. Topological methods and the natural bond orbital scheme are used to rationalize the observed trends. The PA enhancement should be taken into account when dealing with silanols and siloxanes in different environments.