Sound micronutrient management requires an understanding of nutrient interactions and transformation processes in soil–plant systems which can regulate bioavailability and plant uptake. A series of studies were conducted under controlled environment and field conditions to evaluate wheat response to Cu and Zn fertilization on P-deficient soils from western Canada. The grain and straw yields of wheat were reduced in two (Waskada and Tisdale) of three soils used in the controlled environment study, while yield was not affected at the Echo field site in 2016 when both Cu and Zn sulfate fertilizer were applied at 5 kg·ha^–1 rates. Zinc concentration in soil and plant tissues was increased to apparent toxic levels with fertilizer addition in Waskada soils. An imbalance in tissue P:Zn concentration related to micronutrient fertilization was observed in Waskada and Tisdale soils. The availability of Cu and Zn in post-harvest soils was increased with increasing rate of these fertilizers' addition. Chemical and spectroscopic speciation using sequential extraction and X-ray absorption near edge structure, respectively, revealed that Cu and Zn were mostly speciated as carbonate phases, and complexation of these elements with carbonate and phyllosilicate minerals is likely the process controlling bioavailability in the soils.