Several ZnB2O4 powder samples having dopants concentrations of 0.1, 0.01, 0.04 wt% Ce and La were prepared using the nitric acid method via the starting oxides. Several complementary methods such as powder X-ray diffraction (XRD), thermal analyses environmental scanning electron microscopy (ESEM), Radioluminescence (RL) and Cathodoluminescence (CL) techniques were used. Unique luminescence properties of Ce doped ZnB2O4 powder samples are reported for the first time. A new luminescence bands appearing in red part of the spectrum and having all the characteristics of Ce3+ were obtained from RL results. Changing the Ce and La concentration of 0.01-0.1 wt% leads to an increase in RL and CL intensities of Ce3+ and La3+ ions and also CL emission spectra of ZnB2O4 show gradual shift towards longer wavelength. When we compare the luminescence intensity of the samples it is seen that Ce doped ZnB2O4 has the highest intense whereas La doped ZnB2O4 has the lowest one. However, emission spectra of both Ce and La doped samples kept unchanged.