The addition of sludge-based biochar during electrochemical pretreatment of sewage sludge, as an efficient hybrid technology, is potentially to be applied in sludge deep-dewatering. The chars functioned as conductors, catalysts and skeleton particles could enhance the sludge dewaterability and increase the calorific value of the dewatered sludge cake. However, the effect of synthesis conditions on the char properties and further on the dewatering performance is still unknown. Herein, the sludge-based particle electrodes (SPEs) under three main synthesis conditions, including liquid-solid ratio, pyrolysis temperature and time, were prepared. The sludge-based biochars (i.e., SPE-400, SPE-600, and SPE-800 pyrolyzed under 400, 600 and 800 °C, respectively) were characterized and utilized as three-dimensional electrodes during sludge electrolysis. The increased pyrolysis temperature (within 400–800 °C) resulted in the enrichment of metallic ions and increment of specific surface area and pore volume of SPE, which led to the increased catalysis and adsorption sites for viscous proteins (PNs). Particularly, the pores of SPE-800 provided more drainage channels as skeleton builders. Compared with raw sludge, the capillary suction time (CST) and the specific resistance of filtration (SRF) of the treated sludge with 3D-SPE-800 were reduced by 58.12% and 81.01%, respectively, but the net sludge solids yield (YN) was increased by 87.05%. The highest decrease of hydrophilic α-Helix content in PNs (from 9.93% to 7.30%) was observed when using SPE-800 as particle electrode, revealing the crucial role of char characteristics on protein reduction and subsequent dewatering enhancement. The synergistic effects of electrolysis and sludge-based biochar provided a new insight for a closed-loop pretreatment of sewage sludge in the wastewater treatment plant. Display omitted •The sludge char behaved as particle electrodes enhanced electrolysis in improving sludge dewaterability.•The char pyrolysis temperature was highly dependent on sludge dewaterability.•The char functioned as conductors, absorbents, and skeleton particles during electrolysis.•The char favored the reduction of hydrophilic α-Helix in TB-EPS.