The phase composition of the cement paste phase of concrete containing fly ash from circulating fluidized bed combustion (CFBC) was studied. The motivation was to broaden the knowledge concerning the microstructure and the durability of concrete containing new by-products from the power industry. Several air-entrained concrete mixes were designed with constant water to binder ratio and with substitution of a part of the cement by CFBC fly ash (20%, 30% or 40% by weight). X-ray diffraction tests and thermal analysis (DTG, DTA and TG) were performed on cement paste specimens taken from concrete either stored in water at 18° C or subjected to aggressive freeze-thaw cyclic action. The evaluation of the phase composition as a function of CFBC fly ash content revealed significant changes in portlandite content and only slight changes in the content of ettringite. The cyclic freeze-thaw exposure did not have any significant influence on the phase composition of concrete with and without the CFBC fly ash.