Crucial photoemission properties of layered III-V semiconductor cathodes are predicted using Monte Carlo simulations. Using this modeling, a layered GaAs structure is designed to reduce simultaneously the transverse energy and response time of the emitted electrons. This structure, grown by molecular beam epitaxy and activated to negative electron affinity, is characterized. The measured values of quantum efficiency and transverse energy are found to agree well with the simulations. Such advanced layered structures will allow generation of short electron bunches from photoinjectors with superior beam brightness.