Neutron detection technology is widely used in homeland security, nuclear material security detection, and high energy physics, etc. Due to the shortage of ³He resources, it is urgent to develop a novel scintillator that can discriminate neutron and gamma. The Cs₂LaLiBr₆:Ce (CLLB:Ce) crystal has good neutron/gamma discrimination capacity, excellent energy resolution and high light yield, but its neutron/gamma discrimination performance needs further improvement. Here, the CLLB:Ce crystals co-doped with Zr⁴⁺ were grown successfully by the vertical Bridgman method. The results of different characterization methods prove that the Zr⁴⁺ was successfully doped into the matrix and did not effect on the structure of host. Meanwhile, no new luminescence center was generated after Zr⁴⁺ doping. The UV decay time is about 27 ns, presenting a fast fluorescence decay. Figure of merit (FOM) of CLLB:Ce crystal is enhanced from 1.2 to 1.5 by co-doping Zr⁴⁺, which means that the neutron/gamma discrimination performance of CLLB:Ce crystals is improved. Combined with the thermal stability and scintillation decay time, relationship between decay time and FOM was also analyzed. The co-doping of Zr⁴⁺ can inhibit shallow electron trap and V_K centers, reduce electron trapping-detrapping process, and greatly increase the probability of Ce³⁺ direct capturing electron, which results in a shorter decay time. Data from this study indicate that the CLLB:Ce crystals exhibit a huge application prospect in the field of neutron/gamma detection.