It has always been a hot topic to design an orderly mesoscopic structure in functional materials to tailor the macroscopic properties or realize new functions. The existence of domains in ferroelectric materials has been proven to affect the macroscopic properties, being actively studied in nonlinear optical conversion and piezoelectric effects. However, the high-efficiency photoelectric conversion capability of ferroelectric crystals has not yet been explored. Here, the authors study the orderly arrangement of ferroelectric order in KTa1−xNbxO3 (KTN) perovskite crystals, and design the “head-to-head” domains by tuning the Curie temperature Tc, thereby generating abundant charged domain walls and robust conductive channels for electrons and holes. An ultrahigh ultraviolet photoresponsivity is achieved in the KTN crystal under zero bias voltage, being about four orders magnitude higher than that of the well-known ferroelectric materials. The substantial improvement can be attributed to the judiciously designed ferroelectric order, as demonstrated by the conductive atomic force microscopy. In addition, KTN detector exhibits high stability and reliability after high-temperature and fatigue treatment. KTN crystal features giant photoresponsivity, high electric–optical coefficient, and large χ(2) nonlinearity concurrently, indicating its great potential for application of all-optical devices on photonic chips.