In this paper, a metal layer assisted guide mode resonance (MaGMR) device with high sensitivity is proposed for bioanalytical applications and its functioning is experimentally proved. We find that the reflection spectra present a unique inversed response. The resonance mechanism is also discussed. Numerical calculation results indicate that the high sensitivity performance of MaGMR comes from the strongly asymmetric resonance modal profile and low propagation angle inside the waveguide. There is a one-fold enhancement of the evanescent wave in the analytes region compared to typical GMR. According to the experimental results, the proposed MaGMR achieved a bulk sensitivity of 376.78 nm/RIU in fundamental TM mode resonating at 0.809 μm with the first diffraction angle. Experiment results show a 264.78% enhancement in the sensitivity compared to that of the typical GMR sensor in the same resonance conditions of TM mode.