In this work, a methodology for the tabulation of combustion mechanisms via Artificial Neural Networks (ANNs) is presented. The objective of the methodology is to train the ANN using samples generated via an abstract problem, such that they span the composition space of a family of combustion problems. The abstract problem in this case is an ensemble of laminar flamelets with an artificial pilot in mixture fraction space to emulate ignition, of varying strain rate up to well into the extinction range. The composition space thus covered anticipates the regions visited in a typical simulation of a non-premixed flame. The ANN training consists of two-stage process: clustering of the composition space into subdomains using the Self-Organising Map (SOM) and regression within each subdomain via the multilayer Perceptron (MLP). The approach is then employed to tabulate a mechanism of CH 4-air combustion, based on GRI 1.2 and reduced via Rate-Controlled Constrained Equilibrium (RCCE) and Computational Singular Perturbation (CSP). The mechanism is then applied to simulate the Sydney Flame L, a turbulent non-premixed flame that features significant levels of local extinction and re-ignition. The flow field is resolved through Large Eddy Simulation (LES), while the transported Probability Density Function (PDF) approach is employed for modelling the turbulence-chemistry interaction and solved numerically via the Stochastic Fields method. Results demonstrate reasonable agreement with experiments, indicating that the SOM-MLP approach provides a good representation of the composition space, while the great savings in CPU time allow for a simulation to be performed with a comprehensive combustion model, such as the LES-PDF, with modest CPU resources such as a workstation.