We have theoretically investigated a generation of entangled photons from biexcitons in a semiconductor film with thickness in nano-to-bulk crossover regime. In contrast to the cases of quantum dots and bulk materials, we can highly control the generated state of entangled photons by the design of peculiar energy structure of exciton-photon coupled modes in the thickness range between nanometers and micrometers. Owing to the enhancement of radiative decay rate of excitons at this thickness range, the statistical accuracy of generated photon pairs can be increased beyond the trade-off problem with the signal intensity. Implementing an optical cavity structure, the generation efficiency can be enhanced with keeping the high statistical accuracy.