Microbial immobilization is a new strategy for bio-remediation of heavy metals. However, information regarding immobilization of wild resistant bacteria onto biochar for heavy metal separation is limited. This study proposed the use of wild-resistant bacteria TJ6 in combination with biochar produced from agricultural waste (BC-TJ6) for Pb removal and investigated the associated mechanisms using Fourier transform infrared spectroscopy (FT-IR), energy dispersive spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). Compared with the theoretical adsorption capacity according to the linear combination calculating by the mass ratio and adsorption capacity of individual component in the composite material, the actual adsorption capacity of BC-TJ6 for Pb(II) was increased by 73.54%. Specifically, the bridge between the bacteria and biochar of Pb(II) may explain the higher observed adsorption capacity of BC-TJ6 compared to theoretical values. EDS analysis based on electron micrograph showed that Pb(II) adsorbed onto TJ6 strain was 0.48%, while that onto biochar component was 0.14%. It indicated that the resistant bacteria contributed more to the adsorption of Pb(II) in BC-TJ6 composites. The FT-IR analysis suggested that the amide, carboxyl, and hydroxyl groups on the surface of the composite were involved in the adsorption of Pb(II). Further, XPS analysis demonstrated that Pb-O (42.12%) and Pb-OOC (27.6%) were the main Pb-molecular structures bound to the surface of the composite. This study is significant for improving the understanding of biochar-wild resistant bacterial combinations for heavy metal adsorption, and can provide guidance for the use of biochar-microbial remediation of heavy metal pollution.