Elliptical diesel nozzles affect the fuel–air mixing process, and thus combustion and exhaust emissions. Experiments were conducted to study biodiesel spray liquid-phase behaviors for elliptical and circular nozzles through the Mie-scattering method under evaporative conditions. Based on the measurements, the results show that the elliptical nozzle spray liquid-phase penetration is smaller than the circular one under steady-state conditions. The deformation and the axis-switching behaviors of the elliptical jet are helpful in accelerating the breakup of the liquid core. Moreover, the injection pressure has little impact on the penetration of the liquid-phase spray for either geometrical orifice. Additionally, increasing the ambient temperature can reduce the penetration of liquid-phase spray, because an increase in temperature increases the rate of evaporation. The differences in steady liquid-phase penetration between circular and elliptical sprays decrease as the ambient temperature increases. Additionally, increasing the backpressure can decrease the liquid-phase penetration. The differences in steady liquid-phase penetration between circular and elliptical nozzles are reduced with the increase in backpressure, probably due to the axis-switching and deformation behaviors of the elliptical jet being restrained under high-backpressure conditions. Finally, the application of an elliptical orifice is beneficial for decreasing the spray liquid-phase penetration, and thus avoiding the fuel impingement in small engine combustion chambers. The lower liquid-phase penetration for elliptical spray indicated higher fuel and air mixture quality, which is helpful for reducing the diesel engine exhaust soot emissions.