We report the first observation of a large pressure-induced enhancement of giant magnetoresistance (GMR) in magnetic multilayers (MML). In Fe/Cr MMLs with the Cr layer thickness of approximately 30 A, a crossover from biquadratic to bilinear interlayer exchange coupling (IEC) was observed by applying pressure, and simultaneously the GMR under high pressure (>2 GPa) was enhanced to be twice as large as that at ambient pressure. The enhanced GMR is attributed to the suppression of the biquadratic IEC by applying pressure, and the electrical resistivity in parallel alignment of magnetization also showed a crossover behavior, suggesting an electronic origin for the observed pressure effects.