Flammability limit is a significant safety issue for industrial processes. A certain amount of flammability limit data for pure hydrocarbons are available in the literature, but for industrial applications, there are conditions including different combinations of fuels at standard and non-standard conditions, in which the flammability limit data are scarce and sometimes unavailable. This research is two-fold: (i) Performing experimental measurements to estimate the lower flammability limits and upper flammability limits of binary hydrocarbon mixtures, conducting experimental data numerical analysis to quantitatively characterize the flammability limits of these mixtures with parameters, such as component compositions, flammability properties of pure hydrocarbons, and thermo-kinetic values; (ii) Estimating flammability limits of binary hydrocarbon mixtures through CFT-V modeling prediction (calculated flame temperature at constant volume), which is based on a comprehensive consideration of energy conservation. For the experimental part, thermal detection was used in this experiment. The experimental results indicate that the experimental results fit Le Chatelier’s Law within experimental uncertainty at the lower flammability limit condition. At the upper flammability limit condition, Le Chatelier’s Law roughly fits the saturated hydrocarbon mixture data, while with mixtures that contain one or more unsaturated components, a modification of Le Chatelier’s is preferred to fit the experimental data. The easy and efficient way to modify Le Chatelier’s Law is to power the molar percentage concentrations of hydrocarbon components. For modeling prediction part, the CFT-V modeling is an extended modification of CAFT modeling at constant volume and is significantly related to the reaction vessel configuration. This modeling prediction is consistent with experimental observation and Le Chatelier’s Law at the concentrations of lower flammability limits. When the quenching effect is negligible, this model can be simplified by ignoring heat loss from the reaction vessel to the external surroundings. Specifically, when the total mole changes in chemical reactions can be neglected and the quenching effect is small, CFTV modeling can be simplified to CAFT modeling.