Designing binder-free and core-shell-like electrode materials with synergistic effects have attracted widespread attention for the development of high-energy density hybrid supercapacitors (HSCs). Herein, binder-free cobalt molybdate nanosheets laminated cobalt phosphate micropetals on nickel foam (CoM NSs@CoP/NF) were facilely prepared for use as an effective battery-type electrode in hybrid SCs. With the multifunctional features, the rationally combined core-shell-like CoM NSs@CoP/NF electrode exhibited a maximum capacity of 886.8 Ah/cm2 at a current density of 5 mA/cm2 with a good rate capability of 64.2% and cycling stability of 87.4% (after 10000 cycles). The high electrochemical performance of hybrid composite could be attributed to the synergistic effects of hierarchical architectures and large accessible electroactive area, which facilitate the fast electron/transportation within the active material and accelerate the redox chemistry process. Utilizing the superior energy storage properties, a pouch-type HSC was fabricated with core-shell-like CoM NSs@CoP-6 h architectures as a battery-type electrode and activated carbon as a capacitive-type electrode in aqueous alkaline electrolyte. The miniature hybrid device exhibited maximum energy and power densities of 0.44 mWh/cm2 and 40.35 mW/cm2, respectively with good cycling stability. Moreover, the HSCs can energize various portable electronic equipment, which demonstrates its suitability for real-time applications.