A Monte Carlo random walk model was developed to simulate the chain structure of amorphous layers in polyethylene. The chains emerging from the orthorhombic crystal lamellae were either folding back tightly (adjacent re-entry) or performing a random walk (obeying phantom chain statistics) forming statistical loops or tie chains. A correct amorphous density (ca. 85% of the crystalline density) was obtained by controlling the probability of tight folding. Important properties like fracture toughness depend on the number of chains covalently linking together the crystalline regions. The model structure was analysed with a novel numerical topology algorithm for calculating the concentration of tie chains and trapped entanglements. The numerical efficiency of the algorithm allowed molecular cubic systems with a side length of 100 nm to be readily analysed on a modern personal computer. Simulations showed that the concentration of trapped entanglements was larger than the concentration of tie chains and that the thickness of the amorphous layer (La) had a greater impact than the crystal thickness (Lc) on the tie-chain concentration. In several other commonly used models, such as the Huang–Brown model, the influence of trapped entanglements and the effect of the La/Lc ratio are neglected. Simulations using as input the morphology data from Patel generated results in agreement with experimental rubber modulus data.