The introduction of heavy metal-free biomass into the sewage sludge (SS) pyrolysis can effectively improve the biochar properties and reduce the bioavailability and toxicity of heavy metals (HMs) in blended biochar. Herein, this study aimed to understand the biochar properties and associated environmental risks of HMs, by comparing the residual contents from the co-pyrolysis of SS with various organic fractions of municipal solid waste (OFMSW) at 550 °C and pyrolysis alone at different temperatures between 350 and 750 °C. The results indicated that, compared with SS pyrolysis alone, co-pyrolysis of SS with various OFMSW (except PVC) lead to lower biochar yields but with higher pH values (increased between 21.80% and 31.70%) and carbon contents (raised between 33.45% and 48.22%) in blended biochars, and the chemical speciation analysis suggested that co-pyrolysis further promoted the HMs transformation into more stable forms which significantly reduce the associated environmental risk of HMs in the blended biochars (the values of RI lower than 55.80). The addition of PVC, however, impeded biochar properties and compromised HMs immobilization during SS pyrolysis.