Pseudocapacitors have received considerable attention, as they possess advantages of both rechargeable batteries and electric double layer capacitors. Among various active materials for pseudocapacitors, α-layered double hydroxides (α-TM(OH)2, TM = transition metal) are promising due to their high specific capacities. Yet, irreversible α-to-β phase transitions of α-TM(OH)2 hinder their long-term cyclability, particularly when the TM is nickel. Here, it is reported that binary TM ion mixing can overcome the limited cycle lives of α-TM(OH)2 by stabilizing the octahedral frameworks of α-TM(OH)2. In particular, an α-TM(OH)2 with equal amounts of nickel and cobalt exhibits long-term capacity retention (89.0% after 2000 cycles) and specific capacity (206 mAh/g), which are better than those of individual TM counterparts. A series of analyses reveals that the improved performances originate from the synergistic effects between the TM ions; the preferred trivalent state of cobalt ions stabilizes the octahedral framework by accommodating the detrimental Jahn–Teller distortion of Ni3+. The stabilized framework also widens the redox swing range of the nickel up to 4+, thus, increasing the specific capacity of the corresponding α-TM(OH)2. This study indicates that proper mixing of TMs is a prolific approach in enhancing the vital properties of α-TM(OH)2, a promising family of pseudocapacitor materials. Keywords: Layered Double Hydroxide, Electrochemistry, X-ray Absorption Fine Structure Analysis, Crystal Field Theory (Ref) Ji Hoon Lee et al., Adv. Funct. Mater., 2017, DOI:10.1002/adfm.201605225)