Gas flaring is used as an alternative to venting when waste gases cannot be captured from industrial processes such as oil and natural gas production, chemical processing, and waste management. In the oil and natural gas production sector alone, an estimated 3.5 % of total global natural gas production is flared. Survey studies have shown that the methane destruction efficiency (DE) of flares is lower than expected due to real-world conditions (weather and equipment malfunction) and estimate that improving flare efficiency is a 0.5 Tg/yr methane emissions reduction opportunity. Continuous monitoring of flare DE would provide the opportunity for feedback to lower emissions; however, there are currently no technologies used at scale that can provide such a measurement. Here we present a method for measuring the operational methane DE from flares by monitoring methane levels in flares using dual-frequency comb spectroscopy. This method leverages the temperature-dependent absorption fingerprint of methane to differentiate heated and ambient methane. We assess the capabilities of this technique through a set of laboratory-based experiments utilizing a partially premixed methane flame. We estimate the limit of detection (LOD) and sensitivity of the measurements for directly monitoring a flame, and monitoring a flame from a distance of 1 km in the presence of ambient methane. For our configuration, a targeted monitoring scenario (direct flame measurement) results in the ability to distinguish methane DE up to 99.9 %; whereas in the presence of a 1 km background methane signal, the approach is able to quantify methane DE to 97.5 %. These performance metrics could be improved through an updated high-temperature spectral absorption database for methane, however the current estimated performance could already substantially impact flare emissions by closing the gap between the flare design specifications and what research studies estimate from actual in-field performance.