Epoxy resins are increasingly finding applications in the field of structural engineering. A wide variety of epoxy resins are available, and some of them are characterized by relatively low toughness. Several approaches to improve epoxy resin toughness include the addition of fillers, rubber particles, thermoplastics, or their hybrids, as well as interpenetrating networks and flexibilizers, such as polyols. It seems that this last approach did not receive much attention. So in an attempt to fill this gap, the present work deals with the use of hydroxyl-terminated polyester resins as toughening agents for epoxy resin. For this purpose, the modifier, that is, a hydroxyl terminated polyester resin (commercially referred to as Desmophen), which is a polyol, has been used at different concentrations. The prepared modified structure has been characterized using Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) prior to mechanical testing in terms of impact strength and toughness. Two types of Desmophen (800 and 1200) have been used as modifiers. The obtained results showed that hydroxyl-terminated polyester improves the epoxy toughness. In fact, the impact strength increases with Desmophen content and reaches a maximum value of 7.65 J/m at 10 phr for Desmophen 800 and 9.36 J/m at 7.5 phr for Desmophen 1200, respectively. At a critical concentration (7.5 phr), Desmophen 1200 (with higher molecular weight, longer chains, and lower branching) leads to better results. Concerning K-c, the effect of Desmophen 800 is almost negligible; whereas a drastic effect is observed with Desmophen 1200 as K-c reaches a maximum of 2.41 MPa m(1/2), compared to 0.9 MPa m(1/2) of the unmodified epoxy prior to decreasing. This is attributed to the intensive hydrogen bonding between epoxy and Desmophen 1200, as revealed by FTIR spectroscopy. Finally, the SEM analysis results suggested that the possible toughening mechanism for the epoxy resin being considered, which might prevail, is through localized plastic shear yielding induced by the presence of the Desmophen particles.