We investigated the high-purity entangled photon-pair generation in five kinds of “non-poled” potassium titanyl phosphate (KTP) isomorphs (i.e., KTiOPO4, RbTiOPO4, KTiOAsO4, RbTiOAsO4, and CsTiOAsO4). The technique is based on the spontaneous parametric down-conversion (SPDC) under Type II extended phase matching (EPM), where the phase matching and the group velocity matching are simultaneously achieved between the interacting photons in non-poled crystals rather than periodically poled (PP) KTPs that are widely used for quantum experiments. We discussed both theoretically and numerically all aspects required to generate photon pairs in non-poled KTP isomorphs, in terms of the range of the beam propagation direction (or the spectral range of photons) and the corresponding effective nonlinearities and beam walk-offs. We showed that the SPDC efficiency can be increased in non-poled KTP isomorphs by 29% to 77% compared to PPKTP cases. The joint spectral analyses showed that photon pairs can be generated with high purities of 0.995–0.997 with proper pump filtering. In contrast to the PPKTP case, where the EPM is achieved only at one specific wavelength, the spectral position of photon pairs in the non-poled KTP isomorphs can be chosen over the wide range of 1883.8–2068.1 nm.