Carbon fibre (CF), carbon nanotube (CNT), nano-clay (NanoC), and 3D-glass (3DG) reinforced polymer composites were selected to undergo treatment with an accelerated Low Earth Orbit (LEO) simulated space environment. Surface degradation mechanisms of the selected polymer composites with different types of reinforcements are discussed. The extent of the oxidation reaction at the surface as a result of LEO exposure was linked to the increase in the intensity of the oxygen-containing ions, as revealed by time-of-flight secondary ion mass spectrometry (ToF-SIMS). X-ray photoelectron spectroscopy (XPS) indicated that an increasing duration of surface treatment correlates with increasing oxygen concentration and decreasing carbon concentration. The degraded CF composite showed the least amount of oxygen (15.6%) and nitrogen (2.5%) on the surface, likely indicating less surface degradation. Further, XPS high resolution region scans showed decreases in the overall carbon concentration accompanied increases in oxygen-containing carbon species C–O, CO and O–CO; functional groups which are attributed to the LEO treatment of the composite materials. All the sample surfaces were eroded upon exposure to LEO conditions with erosion mostly confined to encapsulating epoxy resin.