The combined effects of transport and fuel reactivity on the critical flame initiation radius for n-alkanes and aromatics are investigated experimentally and numerically using outwardly propagating spherical flames at atmospheric pressure. The effects of transport on the critical flame initiation radius are examined by comparing n-alkanes with different sizes (n-heptane vs. n-decane) but similar molecular structure and reactivity. The effect of fuel reactivity and chemistry on the flame initiation radius are investigated by comparing two alkylated benzene isomers, 1,3,5-trimethylbenzene and n-propylbenzene, which have distinctive reactivity and molecular structures but have the same molecular size and transport properties. The results showed that for n-alkanes, consistent with theoretical predictions, the effect of transport on the critical flame initiation is small for large hydrocarbon fuels. For aromatic fuels, it is found that fuel reactivity defined by fuel molecular structure has a significant impact on the critical flame initiation radius. This observation also supports the theoretical prediction. The results show that fuel with lower reactivity (1,3,5-trimethylbenzene) has a larger critical radius than that with higher reactivity (n-propylbenzene). It is also demonstrated that there is a linear correlation between the critical strain rate and the peak in-flame OH concentration. A radical index combined with transport-weighted enthalpy is proposed to correlate the critical radius of all tested alkanes and aromatic fuels. It is found that the critical radius of all fuels can be reasonably correlated to the product of the radical index and the transport-weighted enthalpy. The results reveal that, similar to flame extinction limits, the critical radius is subject to the combined effect of enthalpy transport and fuel reactivity. The present results suggest that an increase of the product of the transport weighted enthalpy and fuel reactivity may lead to lower chance of ignition failure in internal combustion engines and turbine engine relight.