Summary: Degradation of a polymer in a reactor by the degrading agent(s) follows a distinct pattern, primarily influenced by structural integrity and reactor environment. This distinct pattern is recorded in the changes in the evolved molecular weight distribution (MWD) or polymer chain length distribution (PCLD) curve characteristics from the initial intact state. Modern size exclusion chromatography (SEC) is the best laboratory‐based method that can clearly provide these plots in the form of chromatogram; however, detailed molecular information is not available. The nature of molecular destruction can be well‐characterised if the distinct MWD shift patterns can be simulated to fingerprint the different chain scission dynamics. This is investigated by our current research using the power of computer simulation techniques to gain insight into the polymer ageing processes. One such technique for studying simple decay processes is presented here, and the results are compared with experimental findings. The concept of a binary tree scission model is introduced to show chain rupture as a sequence of probabilistic events and as a non‐linear function of time. Two new mathematical algorithms, an iterative Monte Carlo structured probability scheme and a semi‐iterative algebraic exact statistical formulation method, are investigated to implement this model and simulate the evolution of resultant temporal MW distribution. The latter, an innovative approach to mathematical modelling, has the potential to generate a statistically perfect instant MWD decay curve. A statistical comparison of the product yield is presented from the data obtained using a wide variety of simulated scission regimes to determine the sources of variability.Simulated MWD lateral shift for percent cut scission model showing deviation from the initial MWD (red) over degradation time zones Tj(0 ≥ j ≤ 9) with bimodal and curve broadening effect due to accumulation of varied percent cut range 5–30%.imageSimulated MWD lateral shift for percent cut scission model showing deviation from the initial MWD (red) over degradation time zones Tj(0 ≥ j ≤ 9) with bimodal and curve broadening effect due to accumulation of varied percent cut range 5–30%.