An experimental study was conducted to investigate the relationship between global equivalence ratio(GER) and fire characteristics in an ISO 9705 room. Heptane fuel was burned with different fuel flow rates and doorway widths in order to force the room to be placed in different GER conditions. It was observed that after the onset of under-ventilated fire conditions, temperature and unburned fuel components such as CO and soot increased with increasing heat release rate (HRR), regardless of the doorway width. From the analysis of local mixture fraction, it was reconfirmed that the inclusion of soot production in the product composition was very important to predict accurately the chemical conditions inside the compartment, particularly for the under-ventilated fire conditions. In addition, the local equivalence ratio (LER) was directly proportional to the GER with a unit gradient regardless of doorway width when the soot production was included in the chemical products. This finding provided an important potential that the GER could be used to correlate the local thermal and chemical environment measured at the upper layer of a full-scale enclosure when soot was included.