One-dimensional Ce3+ and Tb3+-co-doped La2O3 (La2O3: Ce/Tb) nanofibres were formed using a simple electrospinning technique followed by a calcination process. XRD, SEM, TEM, and photoluminescence (PL) are used to characterise the resulting samples. Through a heat-treatment process at high temperature, the as-prepared samples are well-crystallised with the hexagonal La2O3 structure. The energy transfer process from Ce3+ to Tb3+ in La2O3: Ce3+/Tb3+ nanofibres was also studied at fixed Ce3+ concentrations and changed Tb3+ concentration. The results show that the green light of Tb3+ became stronger with the increase of Tb3+ concentrations. The fluorescence lifetime of Tb3+5D0 level first increases with the increase of doping concentration and reaches its maximum at 10 mol%, and then decreases.