The Precambrian–Paleozoic boundary in the subsurface of southwestern Ontario commonly is characterized by secondary K-feldspar. In the weathered and altered Precambrian granitoid gneisses at the unconformity, secondary K-feldspar has replaced preexisting minerals, and also occurs as discrete crystals of adularia, overgrowths on altered minerals, and microcrystalline veinlets. The K-feldspar is chemically pure (Or99–100) and has high δ18O values (+18.9 to +21.4‰ Vienna Standard Mean Ocean Water), features that indicate crystallization at low temperatures. Secondary K-feldspar also occurs in Cambro-Ordovician clastic and carbonate rocks that immediately overlie the Precambrian basement. K/Ar (453 ± 9 to 412 ± 8 Ma) and Rb/Sr (440 ± 50 Ma) dates obtained for secondary K-feldspar from the Precambrian host rocks suggest that its crystallization is unrelated to Precambrian weathering or early diagenesis of the immediately overlying Cambro-Ordovician strata. Estimated crystallization temperatures for the secondary K-feldspar (≥100 °C) exceed presumed burial temperatures for the Precambrian–Paleozoic boundary in southwestern Ontario during Late Ordovician–Silurian time. We infer that secondary K-feldspar formed from a hot brine that moved preferentially along the Precambrian–Paleozoic unconformity. The wide distribution of secondary K-feldspar of Late Ordovician–Silurian age throughout mid-continental North America at the Precambrian–Paleozoic boundary records the regional extent of this process. Some Cambro-Ordovician rocks elsewhere in the mid-continent also contain secondary K-feldspar and illitic clay of Late Pennsylvanian–Early Permian age, suggesting more than one episode of fluid movement. Major pulses of orogenic activity may have initiated brine migration. We speculate that the brine originated as connate (sea) water trapped in lower Paleozoic strata, and was modified by rock–water interaction at elevated temperatures, and by mixing with meteoric water.