The effect of diboron trioxide(B;O;) on the crushing strength and smelting mechanism of high-chromium vanadium–titanium magnetite pellets was investigated in this work. The main characterization methods were X-ray fluorescence, inductively coupled plasma–atomic emission spectroscopy, mercury injection porosimetry, X-ray diffraction, metallographic microscopy, and scanning electron microscopy–energy-dispersive X-ray spectroscopy. The results showed that the crushing strength increased greatly with increasing B;O;content and that the increase in crushing strength was strongly correlated with a decrease in porosity, the formation of liquid phases, and the growth and recrystallization consolidation of hematite crystalline grains. The smelting properties were measured under simulated blast furnace conditions; the results showed that the smelting properties within a certain B;O;content range were improved and optimized except in the softening stage. The valuable element B was easily transformed to the slag, and this phenomenon became increasingly evident with increasing B;O;content. The formation of Ti(C,N) was mostly avoided, and the slag and melted iron were separated well during smelting with the addition of B;O;. The size increase of the melted iron was consistent with the gradual optimization of the dripping characteristics with increasing B;O;content.