Geometric magnetic frustration arises when the geometry of a structure prevents the simultaneous fulfillment of nearest-neighbor antiferromagnetic interactions and is commonly observed in lattices that exhibit a triangular topology, such as those found in the pyrochlore structure. Via a mild hydrothermal route, we have synthesized seven quaternary β-pyrochlore-related fluorides AxM2+xM3+(2-x)F6 (A = Cs and Rb; M2+ = Co2+, Ni2+, and Zn2+; and M3+ = V3+ and Fe3+). Crystal structures and compositions were determined using a combination of single-crystal X-ray diffraction and energy-dispersive spectroscopy. After adjusting the reaction conditions, phase-pure products of AxM2+xM3+(2-x)F6 were obtained. The magnetic susceptibility and isothermal magnetization data for all seven compounds were collected to interpret the magnetic behavior, which ranged from paramagnetic to antiferromagnetic with and without a ferromagnetic component. We found that the magnetic behavior of the AxM2+xV3+(2-x)F6 pyrochlore structures strongly depends on the presence or absence of unpaired electrons on the M2+ position. The titled pyrochlore compounds, with the exception of the Zn-analogue, can be considered frustrated materials, with frustration indices in the range of 6-13.