Shear key joints are commonly used in constructions of precast concrete segmental bridges. Most researches focused on shear performance of the dry joints with the identical-strength concrete, leaving a research gap on that of composite joints between different concrete segments. This research aims to investigate shear behavior of shear key joint between reactive powder concrete and high strength concrete. Totally 12 specimens of single-keyed dry joint were tested, with the parameters of concrete compressive strength, steel fibers, and confining stress. The experimental results indicated that shear failure was observed, but crushing phenomenon occasionally occurred in composite joints in testing, which was confirmed by stress distribution from numerical simulation. In terms of shear capacity of composite joint, peak shear loads of reactive powder concrete specimens without steel fibers were enhanced by 10%–12% as increasing of concrete compressive strength, while those with steel fibers achieved 22%–25% enhancement. Nevertheless, a slight reduction of normalized shear strength was obtained because of its lower volume fraction of coarse aggregate. In numerical simulation, as increasing the concrete compressive strength of convex part, peak shear load was enhanced, but the increment rate of peak shear load decreased. Shear design formulae underestimated shear capacity of reactive powder concrete specimens with steel fibers, but the models proposed by Buyukozturk and Rombach gave accurate predictions on those without steel fibers.