Experimental and numerical investigations of burning of horizontal surfaces of poly methyl methacrylate and methyl methacrylate are presented. A burner used in this study allows for the fuel surface to be oriented horizontally at a given distance from the burner rim. One of the aims of this study is to understand the effects of ullage (distance between burner rim and fuel surface) on the burning rate of the fuel and the flame structure. In the case of poly methyl methacrylate, the surface at an initial ullage regresses during its burning, and in the case of methyl methacrylate, the pool level is maintained at the given ullage by supplying the fuel at the rate of its burning. Careful repeatable measurements of temperature and species fields are carried out. These reveal the structure of a small-scale pool flame established over a polymeric fluid such as methyl methacrylate, and such data are scarce in literature. In order to complement the experimental results, fire dynamics simulator is employed to simulate the experimental cases. Flame structure and flow field in the gas phase have been presented and discussed. As the ullage increases, the burning rate decreases. This trend is explained using surface convective heat flux results.