Compactness and large energy conversion capacity are the main reasons of development of sophisticated ceramics materials in microfibers form, which are prepared for high-speed multiferroic systems and devices. These multifunctional composite applications are owing to coupling of electrical and magnetic properties, as well as additional thermal and mechanical properties. So that, they are suitable for magnetic sensors, electrically tunable non-linear transducers, and non-volatile memories. In our experiment, the thin fibers ceramics have been produced using special environmental chamber where the high temperature sintering can be protected by controlling such parameters as temperature and sintering atmosphere. Consequently, for these purposes structural and physical properties, preparation and thermal synthesis of micrometer sized lead lanthanum zirconate titanate (PLZT) fibers were investigated thoroughly. Since the phase transition properties of PLZT fibers differ much, the production process of fibers suffers from lack of proper high temperature control. Consequently, our experiments should help to eliminate this drawback, so that various technological conditions, parameters, and subsequent sintering atmosphere with different mixtures of PbO and ZrO were experimentally tested. Final conclusions include comparative analysis of obtained PLZT fibers ferroelectric phase transition properties to specific sintering atmosphere.