Accurate mathematical models are an essential tool in the development of aftertreatment systems, as they can provide detailed information on the impact of design changes while simultaneously reducing development costs and the time between the initiation and completion of a catalytic process development. Identifying the set of kinetic parameters that achieves a perceived acceptable level of accuracy may require significant time and effort. Optimisation techniques can be used to speed up the tuning process; however, these techniques can require a large computation time, and may not produce a satisfactory answer. This invariably leads to questioning regarding the accuracy of such automated approaches. In this paper, the performance of a number of optimisation algorithms including a GA, nPSO and a hybrid algorithm has been explored with respect to their applicability to kinetic parameters optimisation in the context of aftertreatment modelling. The focus is therefore on the assessment of the optimisers’ performance, rather than the characterisation of catalytic reactions. The different algorithms were applied to the optimisation of parameters in a number of mathematical functions and theoretical aftertreatment systems. The optimisation algorithms were tested on theoretical aftertreatment systems since these have known absolute solutions thereby allowing the optimisers’ performance to be assessed in the absence of any other external source of inaccuracy such as model structure and experimental error. The results obtained demonstrate that such optimisation approaches facilitate the determination of kinetic parameters with suitable accuracy. The proposed hybrid optimisation algorithm achieved excellent performance in considerably shorter computation time than the GA or nPSO optimisers.