Substantial research has been carried out in the literature on direct synthesis of ethanol from syngas. However, ethanol synthesis remains challenging and requires further development. Methanol recycle is of practical interest because the current technologies do not produce a sufficiently low ratio of methanol to C2+ alcohols. Thermodynamic calculations to explore the effect of methanol recycle in a system at chemical equilibrium can offer interesting insights. In this study, a thermodynamic analysis of ethanol synthesis from syngas and by methanol homologation has been performed using the Gibbs free energy minimisation method. The CO conversion and alcohol selectivity are obtained as a function of temperature, pressure, and the initial composition of feedstock. The differences between for the two ethanol synthesis methods are compared. In the direct ethanol synthesis from syngas, high pressure and high H2/CO ratio favour the CO conversion. The temperature has less effect on the CO conversion. Methanol selectivity is a strong function of pressure. The formation of ethanol is favoured by operating reactions at high temperature, high H2/CO ratio, and high pressure. Methanol homologation is found to give better results than the direct ethanol synthesis from syngas. The addition of methanol to syngas does not lead to a significant change in the selectivity of alcohols. However, it greatly affects the CO conversion, resulting in increased yields of alcohols. In addition, the CO conversion decreases until a critical point appears at 0.1 MPa at which the CO conversion remains zero.