Vegetation fires are slightly ionised gaseous medium. Omnipresent alkali metal species in plant's organic structure are the main source of thermally produced electrons in the fires. In the flames, electron-neutral particle collisions dominate other modes of particle interaction. The collision regime absorbs some of the incident energy when the fire is illuminated with electromagnetic waves. The rate of electromagnetic wave absorption in the vegetation fires has implications on the safety of fire-fighters. During wildfire suppression, radio communication blackout at vhf/uhf has been experienced. This may be partly due to thermal ionisation in the fire. In the experiment, the extent of ionisation in vegetation fires is measured using a 2-port vector network analyser. X-band microwaves are caused to propagate combustion zones of eucalyptus bark and guinea grass fires with maximum temperatures of 1114 and 1054 K respectively. Alkali content in the vegetation fuel was different. Measurements show maximum ionisation in flames produced from guinea grass, which had almost twice much potassium as that of eucalyptus bark, to be 2.63 × 1016 m−3 while that produced in eucalyptus bark flame was 1.46 × 1016 m−3.