A magnetically assembled electrode (MAE) is a modular electrode format in electrochemical oxidation wastewater treatment. MAE utilizes magnetic forces to attract the magnetic catalytic auxiliary electrodes (AEs) on the main electrode (ME), which has the advantages of high efficiency and flexible adjustability. However, the issue of the insufficient polarization of the AEs leaves the potential of this electrode underutilized. In this study, natural tourmaline (Tml) particles with pyroelectric and piezoelectric properties were utilized to solve the above issue by harvesting and converting the waste energy (i.e., the joule heating energy and the bubble striking mechanical energy) from the electrolysis environment into additional electrical energy applied on the AEs. Different contents of Tml particles were composited with Fe3O4/Sb-SnO2 particles as novel AEs, and the structure–activity relationship of the novel MAE was investigated by various electrochemical measurements and orthogonal tests of dye wastewater treatment. The results showed that Tml could effectively enhance all electrochemical properties of the electrode. The optimal dye removal rate was obtained by loading the AEs with 0.2 g·cm−2 when the Tml content was 4.5 wt%. The interaction of current density and Tml content had a significant effect on the COD removal rate, and the mineralization capacity of the electrode was significantly enhanced. The findings of this study have unveiled the potential application of minerals and energy conversion materials in the realm of electrochemical oxidation wastewater treatment.