Electron emission from ferroelectrics (FEE) is a promising source for electrons. Although extensive studies have shown that the emission is inititated by a variation of the spontaneous polarization, the exact underlying emission process remained unclear to date. The focus of this work is to analyze and improve the electron emission process from ferroelectric materials. To achieve low operation voltages thin films and low coercive voltage ferroelectric relaxor single crystals were used. The emission was measured under ultrahigh vacuum (UHV) conditions with a single electron detector. The ferroelectric thin films were prepared with a structured top electrode, with nanometer-sized regularly arranged apertures. The emission from lead zirconate titanate (PZT) thin films was achieved at excitation voltages as low as 10 V. The voltage dependent polarization state within the emission apertures of PZT was imaged using piezoresponse force microscopy (PFM). The PFM measurements revealed that an increased fraction of the free surface area is switched by an increased applied voltage. Additional, as a thin film electron emitter, bismuth ferrite (BFO) films were investigated. Ferroelectric relaxor lead magnesium niobate - lead titanate (PMN-PT) was used as single crystal electron emitter due to its low coercive field. The time-dependent electron emission process from PMN-PT was clarified with the help of exciting voltage pulses of variable duration. It is demonstrated that FEE from PMN-PT can be described in the framework of a random field model for relaxors, with the measured electron flux correlating with the amount of reversed polarization. The time-resolved analysis gives insight into the polarization switching and screening processes within PMN-PT. The local electron emission from PMN-PT single crystals has been investigated, in the nanometer regime, with the help of an AFM tip serving as an electron detector. Additionally, the influence of the aperture size in the top electrode on the emission has been investigated. It is found that the electron emission is strongly influenced by the electric field distribution in the aperture. An optimum aperture width for electron emission from PMN-PT, which is much smaller than the apertures used so far, was found. Comparative investigations of the electron emission process from relaxors with barium titanate showed that the emission from PMN-PT is much more complex than the emission from a conventional ferroelectric. General conclusions on the future applications of FEE can be drawn.