Ni(OH)2 electrocatalysts have acquired lots of research attentions as ideal substitutes for noble metals. However, their electrocatalytic performance still cannot meet the demands for applications due to the difficulties in electron transfer and mass transport. According to kinetics principle, the construction of hollow structure is regarded as an effective method to achieve outstanding electrocatalytic performance. In this work, Ni(OH)2 hollow porous architecture (Ni(OH)2 HPA) was simply synthesized through a coordinating etching and precipitating (CEP) method for the building of enzymatic-free glucose sensors. Ni(OH)2 HPA presents large specific surface area (SSA), ordered diffusion channels, and structure stability. As a detection electrode for glucose, Ni(OH)2 HPA exhibits eminent electroactivity in terms of high sensitivity (1843 μA mM−1 cm−2), lower detection limit (0.23 μM), and short response time (1.4 s). The results demonstrate that Ni(OH)2 HPA has practical applications for construction of enzymatic-free electrochemical sensors. The design of hollow structure also provides an effective engineering method for high-performance sensors.Electronic supplementary materialThe online version of this article (10.1186/s11671-018-2726-8) contains supplementary material, which is available to authorized users.