Understanding the structural differences between feedstocks is critical for biochar effectiveness in plant growth. To examine the efficiency of biochars with unique physiological structures in a cadmium (Cd)-polluted soil, rice and maize as C3 and C4 plants, as well as biochar generated from their residues, defined as BC3 and BC4, were utilized. The experiment involved a control and a Cd-polluted soil (20 mg kg−1) without biochar application, and applications of each type of biochar (20 t ha−1) on Cd-polluted or unpolluted soil. In rice and maize fields, BC3 application led to the highest value of cation exchange capacity (CEC), with increases of 162% and 115%, respectively, over the control, while CEC increased by 110% and 71% with BC4 in the rice and maize field, respectively. As compared to the control, BC3 and BC4 dramatically enhanced the photosynthetic rate (Pn) of rice by 116% and 80%, respectively, and maize by 67% and 31%. BC3 and BC4 significantly decreased the Cd transfer coefficient in rice by 54% and 30% and in maize by 45% and 21%. Overall, BC3 is preferred over BC4 for establishing rice and maize in Cd-polluted soil, as it has a lower C/N ratio, a considerably higher surface area, and more notable alkaline features such as a higher CEC and nutrient storage.