The impact of silicon and aluminum on phase transformation behavior, particularly bainite, and microstructure evolution in Fe–0.2C–2.5Mn steel are presented. Continuous–cooling–transformation (CCT) and time–temperature–transformation (TTT) diagrams are determined experimentally. An aluminum extended empirical formula is introduced to estimate the martensite start temperature (Ms) with a thorough assessment of existing formulae. Results show that aluminum significantly increases Ms and has a stronger influence on promoting ferritic microstructures than silicon. During continuous cooling, alongside bainite, formation of Widmanstätten structures is induced in aluminum‐alloyed steel at higher cooling rates due to increased prior austenite grain size. Silicon decelerates bainite transformation kinetics by enhancing austenite's chemical stability through carbon enrichment via preventing carbide precipitation and by strengthening austenite against displacive phase transformation via solid solution hardening. Although aluminum has similar effects, incubation time is shortened during isothermal treatment because of the increased driving force, which overcompensates for the retardation effects. A finer carbide‐free bainitic microstructure is achieved in aluminum‐alloyed steel with more pronounced film‐like retained austenite (RA) formation and superior carbon enrichment, improving RA stability and suppressing martensite–austenite island formation. Finally, with the proposed formula, an accurate approximation to experimental Ms is accomplished.