The method of generating x-rays using the pyroelectric effect has garnered interest for applications that desire portability and low power consumption, particularly for real-time in-field and on-line analyses. However, the x-ray intensity produced by this type of x-ray generator is low and inconsistent compared to conventional x-ray tubes. The properties of several pyroelectric materials, including LiTaO3, LiNbO3, and PMN-xPT, were studied and subsequently tested on an in-house developed x-ray generator to explore their suitability for the application. The production of electrons to subsequently generate x-ray relies on the process of ferroelectric electron emission and field ionization to be dominant over charge compensation via the DC conductivity of the pyroelectric material. Given that the time of temperature change occurs faster than the material's charge relaxation time, it was found that the ratio of the pyroelectric coefficient to relative permittivity determined the performance of the x-ray generator. Thus, the x-ray count rates and end-point energies produced by LiTaO3 showed that it continues to be a strong candidate for such x-ray generation applications.