The properties of biochars derived from different raw materials (rice husk, bamboo, caragana, and garbage) and their effects on the microbial reductive dechlorination of pentachlorophenol (PCP) were investigated to understand how biochars influence the biotransformation of environmental pollutants. The results indicated that only caragana-derived biochar showed stable electron transfer activity for PCP dechlorination. Electro(chemical) analyses revealed that caragana biochar had the highest electrical conductivity (EC) (2.22 × 10⁶ μS cm⁻¹), while those of the other biochars were <1500 μS cm⁻¹. The electron transfer capacities were within the ranges of 61.63–155.83 μmol e⁻ g⁻¹. Cyclic voltammetry analysis suggested that there were no obvious redox peaks for the biochars, while the Fourier transform infrared analysis showed similar transmission spectra with variable absorption intensity; this suggested that all biochars possessed similar structures and functional group classes and the enhancement of PCP dechlorination was not attributable to the redox reaction. Overall, the beneficial effects of caragana biochar on PCP dechlorination depended on the EC rather than the redox functional groups, possibly because high EC values enabled the highest electron transfer, and thus resulted in the greatest promotion of reductive dechlorination activity.