This study investigates the growth dynamics and heavy metal immobilization in Sudan grass cultivated on substrates composed of electrolytic manganese residue (EMR), phosphogypsum, and chili straw biochar. Pot experiments revealed that a substrate with phosphogypsum constituting 75% of the mix hinders Sudan grass seed germination. Compared with sole EMR utilization, the composite substrates notably enhanced plant growth, evidenced by increases in plant height and fresh weight. The integration of these substrates led to a significant elevation in total chlorophyll content (up to 54.39%) and a reduction in malondialdehyde (MDA) levels (up to 21.66%), indicating improved photosynthetic activity and lower oxidative stress. The addition of biochar reduced the content of Zn, Cd, and Mn in the roots of Sudan grass by up to 25.92%, 20.00%, and 43.17%, respectively; and reduced the content of Pb, Mn, and Cr in the shoot by up to 33.72%, 17.53%, and 26.32%, respectively. Fuzzy membership function analysis identified the optimal substrate composition as 75% EMR and 25% phosphogypsum, with 5% chili straw biochar, based on overall performance metrics. This study adopts the concept of “to treat waste with waste”. The approach is to fully consider the fertility characteristics of EMR, phosphogypsum, and biochar, underscoring the potential for utilizing waste-derived materials in cultivating Sudan grass and offering a sustainable approach to plant growth and heavy metal management.