Crystal structure and electrical properties of A2Cu3Ge4O12 (where A = Na, K) have been investigated by neutron diffraction and electrical impedance spectroscopy (EIS). The real and imaginary parts of the impedance, dielectric constant, and electrical modulus have been studied as a function of frequency and temperature. The crystal structures of the compounds K2Cu3Ge4O12 (KCGO) and Na2Cu3Ge4O12 (NCGO) are made of perfect 2D and quasi-2D alkali metal ion layers, respectively. The dc conductivity occurs due to small polaron hopping for both compounds with single activation energy over the entire experimentally available temperature range. The values of activation energies are 0.90(3) and 1.22(6) eV for KCGO and NCGO, respectively, as determined from dc conductivity and relaxation time analysis. The frequency dependent ac conductivity curves for both compounds follow a universal Jonscher’s power law. Soft bond valence sum analysis of neutron diffraction data reveals that the conduction pathways are confined within a plane in KCGO, whereas they form a one-dimensional channel in NCGO. The bottlenecks for ionic conduction and the role of crystal structure on them are discussed. The scaling behavior of electrical modulus indicates that the relaxation process does not change with temperature; however, a sharp decrease in the time constant has been observed. The present comprehensive study facilitates the understanding of the role of crystal structure on the microscopic mechanism of ionic conduction in both battery materials, which would be useful in designing sodium and potassium based ionic conductors. Further, the constant value of activation energy over the kHz frequency range is suitable for potential applications of the studied materials in avalanche beacons and amateur and geophysical sensors.