In this paper, we demonstrate in a clear procedure the application of the Anaerobic Digestion Model No. 1 (ADM1) to model a large-scale covered in-ground anaerobic reactor (Cigar), processing sugarcane vinasse from a biorefinery in Brazil. The biochemical make-up (carbohydrates, proteins, and lipids) of the substrate was analysed based on the food industry standards. Two distinct subsets of data, based on the sugarcane harvest season for bioethanol and sugar production in 2012 and 2014, were used to direct and cross validate the model, respectively. We fitted measured data by estimating two key parameters against biogas flow rate: the degradation extent (fd) and the first order hydrolysis rate coefficient (khyd). By cross validation we show that the fitted model can be generalised to represent the behaviour of the reactor under study. Therefore, motivated by practical and industrial application of ADM1, for both different reactors types and substrates, we show aspects on the implementation of ADM1 to a specific large-scale reactor for anaerobic digestion of sugarcane vinasse.