Manufacturing an economically viable, efficient commercial thermoelectric (TE) module is essential for power generation and refrigeration. However, mediocre TE properties, lack of good mechanical stability of the material, and significant difficulties involved in the manufacturing of large-scale powder as well as bulk samples hinder the potential applications of the modules. Herein, an economically feasible single-step water atomization (WA) is employed to synthesize BST powder (2 kg) by Cu doping within a short time and consolidated into large-scale bulk samples (500 g) for the first time with a diameter of 50 mm and a thickness of about 40 mm using spark plasma sintering (SPS). The incorporation of Cu into BST greatly boosts the carrier concentration, leading to a significant increase in electrical conductivity, and inhibits the bipolar thermal conductivity by 73%. Synchronously, the lattice contribution (κL) is greatly reduced by the effective scattering of phonons by comprising fine-grain boundaries and point defects. Therefore, the peak ZT is shifted to the mid-temperature range and obtained a maximum of ∼1.31 at 425 K and a ZTave of 1.24 from 300 to 500 K for the BSTCu0.05 sample, which are considerably greater than those of the bare BST sample. Moreover, the maximum compressive mechanical strength of large-size samples manufactured by the WA-SPS process is measured as 102 MPa, which is significantly higher than commercial zone melting samples. The thermoelectric module assembled with WA-SPS-synthesized BSTCu0.05 and commercial n-type BTS material manifests an outstanding cooling performance (−19.4 °C), and a maximum output power of 6.91 W is generated at ΔT ∼ 200 K. These results prove that the BSTCux samples are eminently suitable for the fabrication of industrial thermoelectric modules.