We present results of detailed investigation of the crystal structure of Pb1−3x/2Lax(Zr1−yTiy)O3 solid solutions. In this letter our attention is concentrated on the series of solid solutions with x = 6% usually referred to as relaxor ferroelectrics. We have established the reasons for the non-cubic crystal structure of these solid solutions at the temperatures below TC. It is demonstrated that the peculiarities of the properties of Pb1−3x/2Lax(Zr1−yTiy)O3 depend on the position of a particular solid solution with respect to the hysteresis ferroelectric–antiferroelectric region in the ‘Ti-content–temperature’ phase diagram.

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