This work deals with the problem of intermetallic phases in cast standard duplex steel ASTM A890 Gr 4A (generally known as 2205). The investigated steel was subjected to isothermal heat treatment in the range from 595 °C to 900 °C and in the duration from 15 minutes to 245 hours, and was also investigated in terms of anisothermal (natural) cooling after casting into the mould. The precipitation starts at grain boundaries with a consistent ferrite transformation. The work is focused on the precipitation of the sigma phase (σ) and the chi phase (χ). Examination of the microstructure was conducted using light and scanning electron microscopy. Their statistical analysis was carried out using the results of the investigations of precipitation processes in the microstructure, both within the grains and at the grain boundaries. To illustrate this impact, the surface area of precipitates was evaluated. The percentage of these intermetallic phases was calculated by measuring their area using a computer image analysis system. Based on their observations, a combined time-temperature transformation (TTT) diagram with continuous cooling transformation (CCT) curves was created.