Proton exchange membrane fuel cells (PEMFC) connected with a methanol steam reformer designed to enhance its performance is considered as a promising future power source. Enhancing the performance of a cylindrical methanol steam reformer due to diffuser effects was then investigated applying three-dimensional computational fluid dynamics by the SIMPLE-C algorithm and an Arrhenius form of reaction model. The effect of the angle and length of the diffuser, and wall temperature have been explored on heat and fluid flow, methanol conversion, hydrogen production, carbon monoxide reduction, as well as estimated net power of fuel cell with the same catalyst volume and entrance condition in a cylindrical methanol steam reformer. The results indicate that the diffuser obviously enhances methanol conversion and hydrogen production of a cylindrical methanol steam reformer. In comparison with a traditional reformer, the reformer with a diffuser of theta(d) = degrees 6 and L-d = 75 mm obtains the maximum enhancement of 22.96% in methanol conversion, 44.62% in hydrogen production, and 24.59% in estimated net power of fuel cell at wall temperature of 250 degrees C. In addition, the novel reformer with a diffuser of theta(d) = degrees 9 and L-d = 100 mm generates the maximum reduction of 44.17% in CO production at T-w = 250 degrees C.