Broken rice has become more popular to be sustainably used due its low-cost and potential utilization for preparing purified/modified starches and fermented products. The use of broken rice as substrate of an enzymatic extrusion process modified by divalent metal salts was investigated. Six metal salts with concentrations 0.6, 1.2, and 1.8 mmol/100g (db of starch) were premixed with a thermostable α-amylase and with broken rice before being extruded. Extrudates were characterized using RVA, X-ray, FT−IR, and SEM techniques. RVA results showed that Mg(II), Ca(II), Mn(II), and Zn(II) decreased extrudate viscosity whereas Fe(II) and Cu(II) increased it compared to extrusion performed in absence of salts. DNS test demonstrated that nontransition metals Mg(II) and Ca(II) activated the enzyme and improved the extrusion performance, while transition metals Mn(II), Fe(II), Cu(II), and Zn(II) inhibited the activity of the enzyme. X-ray Diffraction (XRD) showed that all ions contributed to slightly increase the extrudate crystallinity. Holes of various sizes were observed on the surface of the extruded material when salts were used, indicating changes in enzymatic action. The residual content of phenolics increased when the ions Mg(II), Ca(II), and Mn(II) were used while the hydrogen (rather than electron) donating capacity of phenolics was slightly influenced.