Radiocarbon (14C) is a powerful tracer of fossil emissions because fossil fuels are entirely depleted in 14C, but observations of 14CO2 and especially 14CH4 in urban regions are sparse. We present the first observations of 14C in both methane (CH4) and carbon dioxide (CO2) in an urban area (London) using a recently developed sampling system. We find that the fossil fraction of CH4 and the atmospheric concentration of fossil CO2 are consistently higher than simulated values using the atmospheric dispersion model NAME coupled with emission inventories. Observed net biospheric uptake in June-July is not well correlated with simulations using the SMURF model with NAME. The results show the partitioning of fossil and biospheric CO2 and CH4 in cities can be evaluated and improved with 14C observations when the nuclear power plants influence is negligible.