The apparent efficacy of linuron to control pigweeds (Amaranthus spp.) has declined in Ontario, Canada, in past decades, possibly due to resistance. Samples were collected in multiple fields across Ontario with reported linuron failure. These were characterized at the whole-plant and molecular levels. Screening with linuron revealed resistance in six out of nine green pigweed (Amaranthus powellii Wats.) populations and 36 out of 38 populations of redroot pigweed (Amaranthus retroflexus L.). Sequencing of the psbA gene showed resistant plants had mutations conferring resistance to photosystem II (PSII) inhibitors. The most commonly seen mutation was coding for a Val₂₁₉Ile substitution, while other populations had Ala₂₅₁Val or Phe₂₇₄Val. Two populations were documented with a double mutation at Val₂₁₉Ile and Phe₂₇₄Val. All substitutions endowed plants with low to moderate resistance to linuron, with various levels of cross resistance to other PSII inhibitors. The double mutants were characterized by higher levels of resistance to linuron and diuron compared with each single substitution. The widespread failure of linuron to control pigweed species in many carrot fields in Ontario is due to the selection of PSII mutants. This is the first report of double mutation in psbA in any weed species and the first report of Ala₂₅₁Val and Phe₂₇₃Val in pigweed species. The presence of a double mutation is probably the result of continuous selection of plants already resistant due to a single mutation. Our results illustrate the need for diversified weed management strategies in crops where herbicide options are limited.