As a highly toxic heavy metal pollutant, mercury ions cause substantial risks to the environment and human health, and developing high-performance and convenient analytical approaches becomes quite important. Here we propose a performance-complementary colorimetric/electrochemical dual-mode Hg2+ sensing method based on the analyte accelerating the peroxidase-mimetic activity of gold nanoparticles (AuNPs) loaded on graphene oxide (GO). The GO-AuNPs composite was readily fabricated via mechanically mixing AuNPs and GO with controllable proportions, exhibiting a weak peroxidase-like activity in catalyzing the oxidation reaction of 3,3′,5,5′-tetramethylbenzidine (TMB). Upon the introduction of Hg2+, it combined with AuNPs rapidly, significantly enhancing the peroxidase-mimicking activity of GO-AuNPs. By capturing the color signal of the generated blue oxTMB and the electro-oxidation response of residual TMB, a “turn-on” colorimetric and “turn-off” electrochemical bimodal method was established for Hg2+ measurement, providing a linear range of 10–60 μg/L in colorimetric detection and 0.001–20 μg/L in electrochemical analysis. Different from common bimodal assays mainly improving detecting reliability due to their cross-validation ability, our dual-mode sensor exhibits the unique feature of complementary sensitivity and detection range, thus enabling its flexible use in analyzing different levels of the target in a broad scope with no requirement for sample enrichment and dilution.