Porous α-Ni(OH)2 microflowers are successfully synthesized via a one-step aqueous-phase reaction assisted by block copolymers under mild conditions. The electrochemical measurement demonstrates that the α-Ni(OH)2 microflowers calcined at 200 °C are capable to deliver a specific capacity of 1551 F g−1 in 6 M KOH solution, suggesting their high potential as a novel electrochemical pseudocapacitor.