Pt electrocatalysts well-dispersed on iron (Fe)-embedded porous carbon nanofiber (CNF) supports were synthesized using electrospinning and a reduction method for improved methanol electrooxidation. To study the effects of the amount of Fe embedded in the porous CNF supports, we used three different amounts of Fe precursor: 4 wt% (sample A), 8 wt% (sample B), and 12 wt% (sample C). Among them, sample B exhibited the highest anodic current density of 619.0 mA/mgp, and excellent electrocatalytic stability compared to commercial Pt/C and Pt/CNFs. The enhanced methanol electro-oxidation performance can be explained by the combined effects of increased active area between the Pt electrocatalysts and the electrolyte due to well-dispersed Pt electrocatalysts on porous CNF supports, and the improved electrical conductivity of the supports due to the efficient electron transfer by Fe nanoparticles embedded within porous CNFs.