Improving the self-conductivity and structural stability of electrode materials is a key strategy to improve the energy density, rate performance, and cycle life of supercapacitors. Controlled intercalation of ethyl carbamate (CH3CH2OCONH2) as the rivet between Ni-Co hydroxide layers can be used to obtain sufficient ion transport channels and robust structural stability of hydrangea-like α-Ni1/3Co2/3(OH)2 (NC). Combining the improved electronic conductivity offered by the coexistence of Ni2+ and Co2+ optimizing itself electronic conductivity and the addition of carbon nanotubes (CNTs) as the electron transport bridge between the active material and the current collector and the large specific surface area (296 m2 g-1) reducing the concentration polarization, the capacitance retention ratio of NC-CNT from 0.2 to 20 A g-1 is up to 93.4% and its specific capacitance is as high as 1228.7 F g-1 at 20 A g-1. The large total hole volume (0.40 cm3 g-1) and wide crystal plane spacing (0.71 nm) provide an adequate space to withstand structure deformation during charge/discharge processes and enhance the structural stability of the NC material. The capacitance fading ratio of NC-CNT is only 4.5% at 10 A g-1 for 10 000 cycles. The aqueous supercapacitor (NC-CNT//AC) and all-solid-state supercapacitor (PVA-NC-CNT//PVA-AC) exhibit high energy density (35.2 W h kg-1 at 100.0 W kg-1 and 35.4 W h kg-1 at 100.7 W kg-1), ultrahigh rate performance (the specific capacitances at 20 A g-1 are 92.8 and 87.2% compared to that at 0.5 A g-1), and long cycling life span (the specific capacitances after 100 000 cycles at 10 A g-1 are 91.5 and 90.8% compared with that of their initial specific capacitances), respectively. Therefore, hydrangea-like NC could be a promising material for advanced next-generation supercapacitors.