The aim of this study is to develop a model predictive controller (MPC) accompanied with a metabolic reaction model controller for controlling ethanol and n-pentanol concentrations and the mole fraction of monomer units in the production of poly(beta-hydroxybutyrate-co-beta-hydroxyvalerate), P(HB-co-HV), a biodegradable copolyester. The controller consists of two parts: one is for alcohol concentration control and the other one is for mole fraction control, and is based on the concept of metabolic flux distribution control. For control of alcohol concentration, conventional proportional and integral (PI) controller and feedforward/feedback controller did not function sufficiently because the large sampling interval of the biosensor led to a severe overshoot of concentration. A single-input and single-output (SISO) MPC is constructed for control of ethanol concentration in the growth phase, whereas a multi-input and multi-output (MIMO) MPC is constructed for control of both alcohol concentrations in the production phase. Specific ethanol consumption rate was estimated by the MPC using the past time series data of ethanol concentration. By means of simulations and experiments, the weighting parameters of the noise filters in the MPC were well adjusted. Ethanol and n-pentanol concentrations were well controlled by the MPC, compared with PI controller and feedforward/feedback controller. As a result, P(HB-co-HV) production was maximized with a given value of mole fraction of 3HV units at the end of cultivation.