In order to mitigate the detrimental impact that climate change is having on plants, the study of new practices that allow for the reduction of such effects has become imperative. In addition, the revaluation of the promotion of healthy plant by-products has also markedly increased in importance in recent years. In this work, the modifications in biomass and some antioxidant compounds of cauliflower by-products treated with putrescine under extreme temperatures in two different CO2 scenarios (the control (400 ppm) and a high concentration of CO2 (1000 ppm)) were studied. Additionally, the compositions of inner and outer leaves were also compared. According to results found in this work, cauliflower grown under elevated CO2 and treated with putrescine (2.5 mM) prior to heat stress showed the highest biomass accumulation (20%) compared to the control. Moreover, in the outer leaves from cauliflower grown under elevated CO2 and treated with putrescine prior to high temperature exposure, the highest biosynthesis of sugars (20%) was recorded. Although cauliflower by-products turned out to be rich in polyamines (208.6 nmoles g-1 fresh weight (FW) and 124.3 nmoles g-1 FW for outer and inner leaves, respectively) and phenolic compounds (1070.2 mg gallic acid equivalents ( (GAE) 100 g-1 FW in outer leaves and 772.0 mg GAE 100 g-1 FW in inner leaves), it was the outer leaves that after applying the new strategy showed the greatest increase in polyamines (68%) and phenolic compounds (39%), obtaining here the highest increase in antioxidant activity (3%). Thus, they should no longer be regarded as mere by-products and should be used for pharmaceutical or nutraceutical purposes. The novel strategy presented in this work may allow us to take advantage of both the continued increase in CO2 and heat waves that are becoming more frequent.