The preparation of nanozymes with high specific activity is highly important for various applications. However, only a few nanozymes have specific activities comparable to natural enzymes. Herein, novel Pt-on-Rh hollow nanorods (PtRh HNRs) were developed, in which surface Pt exhibited adjustable dispersity and interior Rh served as the support. The optimized PtRh HNRs demonstrated high-performance peroxidase (POD)-like activity, with a specific activity as high as 1352 U mg-1, which was 3.86 times that of their monometallic Pt counterparts. Density functional theory (DFT) calculations illustrated that the presence of Rh decreased the energy barrier of the rate-determining step. When PtRh HNRs were used as nanozymes in the colorimetric detection of hydrogen peroxide (H2O2) and ascorbic acid (AA), the limits of detection (LODs) were as low as 9.97 μM and 0.039 μM, respectively. The current work highlights a facile and powerful strategy for manufacturing nanozymes with high specific activity and demonstrates that the prepared PtRh HNRs have the potential for analysis and determination.