This research explores the photofermentation of glycerol to hydrogen by Rhodopseudomonus palustris, with the objective to maximise hydrogen production. Two piecevvise models are designed to simulate the entire growth phase of R. palustris; a challenge that few dynamic models can accomplish. The parameters in both models were fitted by the present batch experiments through the solution of the underlying optimal control problems by means of stable and accurate discretisation techniques It was found that an initial glutamate to glycerol ratio of 025 was optimal and was independent of the initial biomass concentration. The glycerol conversion efficiency was found to depend on initial biomass concentration and its computational peak is 64.4%. By optimising a 30 day industrially relevant batch process, the hydrogen productivity was improved to be 37.7 mL g biomass(-1) h(-1) and the glycerol conversion efficiency was maintained at 58%. The models can then be applied as the connection to transfer biohydrogen production from laboratory scale into industrial scale. (C) 2015 Elsevier Ltd. All rights reserved.