This work examined the capability of Imperata cylindrica to respond, tolerate and accumulate Cu when growing at high Cu concentration (300 mg kg−1 of substrate) at different times of exposure (2, 14 and 21 days). The Cu accumulation in plants was examined by atomic absorption spectroscopy (AAS) and Cu localized by Scanning Electron Microscopy-Energy Dispersive X-Ray spectroscopy. Additionally, the phenolic compound identifications and concentrations were determined using liquid chromatography coupled to mass spectrometry. Our results showed that root biomass decreased significantly at high Cu levels, with a greater decrease at 21 days (39.8% less biomass in comparison to control). The root showed 328 mg Cu kg−1 dry weight at 21 days of exposure to Cu, being the tissue that accumulates most of the Cu. Lipid peroxidation was a clear indicator of Cu stress, principally in shoots. The exposure to Cu significantly increased the synthesis of phenolic compounds in shoots of plants exposed 21 days to Cu, where 5-caffeoylquinic acid reached the highest concentrations. Our results support that I. cylindrica is a Cu accumulator plant in root organs with a medium level of accumulation (between 200–600 mg Cu kg−1 biomass), which can tolerate the exposure to high Cu levels by means of increasing the synthesis of phenolic compound in shoots, suggesting a potential use as phytoremediation tool in Cu polluted environments.