One new metal borate-phosphate, CsZn4(BO3)(PO4)(2), and two new metal phosphates, CsZn4(PO4)(3) and RbZn4(PO4)(3), have successfully been synthesized by spontaneous crystallization with molten fluxes, and their structures were determined by single-crystal X-ray diffraction. These compounds exhibited three-dimensional frameworks; stacking of unique (1)(infinity)[Zn4BO11] mirror-image chains and isolated PO4 tetrahedra for CsZn4(BO3)(PO4)(2), and (1)(infinity)[Zn4PO12] chains and isolated PO4 tetrahedra for CsZn4(PO4)(3) and RbZn4(PO4)(3). Interestingly, (1)(infinity)[Zn4BO11] is the first example in which the B atoms locate on the mirror axis of the image-symmetrical (1)(infinity)[Zn4O11] chains. Structure comparisons show that the substitution of BO3-PO4 is a feasible strategy for preparing new compounds, and the M/(B + P) ratio of compounds is a factor affecting the existence form of the anionic groups. Infrared spectra, thermal analysis, UV-vis-NIR diffuse reflectance spectroscopy, and first-principles calculations of the above three compounds are reported in this work.