The rapid development of GaAs photocathodes has led to an increased focus on the attainment of high quantum efficiency. Three types of exponential-doping structures with a high to low doping concentration distribution from the interior to the surface are proposed for reflective GaAs emission layers. These three structures generate different built-in electric fields that facilitate photoelectron emission. The one-dimensional continuity equations for the increasing, constant, and decreasing types of built-in electric fields are derived, respectively. The electron concentration distribution and quantum efficiency varying with the wavelength are solved numerically by the finite difference method. The simulation results indicate that the quantum efficiency of the GaAs photocathode with the increasing type of built-in electric field is superior to that with the constant built-in electric field, while the GaAs photocathode with the decreasing type of built-in electric field shows the worst performance. Then, the designed GaAs photocathodes with the increasing and constant types of built-in electric fields are grown by metal-organic chemical vapor deposition and activated by cesium-oxygen alternating deposition. The measured spectral response curves show that the quantum efficiency of the GaAs photocathode with the increasing type of built-in electric field is higher in the whole band than that with the constant type of built-in electric field. In addition, the exponential-doping structure generating the increasing type of built-in electric field is beneficial for improving the surface potential barrier and increasing the surface electron escape probability.