Characteristics of the microstructure of corrosion-resistant cast 24Cr-5Ni-2.5Mo duplex steel after introduction of 0.98, 1.67 and 4.3% Si were described. Based on the test results it has been found that silicon addition introduced to the corrosion-resistant cast two-phase duplex steel significantly reduces austenite content in the alloy matrix. Increasing silicon content in the test alloy to 4.3% has resulted, in addition to the elimination of austenite, also in the precipitation of Si-containing intermetallic phases at the grain boundaries and inside the grains. The precipitates were characterized by varying content of Cr and Mo, indicating the presence in the structure of more than one type of the brittle phase characteristic for this group of materials. The simulation using Thermo-Calc software has confirmed the presence of ferrite in all tested alloys. In the material containing 4.3% Si, the Cr and Si enriched precipitates, such as G phase and Cr3Si were additionally observed to occur.