In the present study, we successfully prepared two different electrospun polyacrylonitrile (PAN) based-activated carbon nanofiber (ACNF) composites by incorporation of well-distributed Fe2O3 and Co3O4 nanoparticles (NPs). The influence of metal oxide on the structural, morphological, and textural properties of final composites was thoroughly investigated. The results showed that the morphological and textural properties could be easily tuned by changing the metal oxide NPs. Even though, the ACNF composites were not chemically activated by any activation agent, they presented relatively high surface areas (SBET) calculated by Brunauer-Emmett-Teller (BET) equation as 212.21 and 185.12 m2/g for ACNF/Fe2O3 and ACNF/Co3O4 composites, respectively. Furthermore, the ACNF composites were utilized as candidate adsorbents for CO2 and CH4 adsorption. The ACNF/Fe2O3 and ACNF/Co3O4 composites resulted the highest CO2 adsorption capacities of 1.502 and 2.166 mmol/g at 0 °C, respectively, whereas the highest CH4 adsorption capacities were obtained to be 0.516 and 0.661 mmol/g at 0 °C by ACNF/Fe2O3 and ACNF/Co3O4 composites, respectively. The isosteric heats calculated lower than 80 kJ/mol showed that the adsorption processes of CO2 and CH4 were mainly dominated by physical adsorption for both ACNF composites. Our findings indicated that ACNF-metal oxide composites are useful materials for designing of CO2 and CH4 adsorption systems.