Composite structures exhibiting magnetoelectric (ME) coupling behavior have applications in various fields such as energy harvesting, sensors and actuators. ME coupling behavior is considered to occur by transfer of strain through bonding of the constituent phases of the ME composite. Here, the influence of thermal environment on the constitutive behavior of ferroic phases was examined, firstly by conducting experiments at various temperatures. To mimic the constitutive behavior of ferroic phases, constitutive models were built based on a thermodynamic framework. In order to account for thermal effects, appropriate functions were introduced to the formulation. Model parameters were chosen based on experimental data and simulation studies were performed. The obtained results were found to be in agreement with the experiments. Additionally, an attempt was made to capture the mechanical, electrical, magnetic and ME coupling behavior of composites. To capture the response of ME composites, a homogenization technique was employed along with the proposed constitutive relation for the constituent phases of an ME composite. © 2017 IOP Publishing Ltd.