Based on the band transport model, the two-center nonvolatile holographic recording in (Ce,Cu)∶LiNbO3 has been theoretically investigated and optimized. Microphysical parameters of (Ce,Cu)∶LiNbO3 crystal are obtained and used to rigorously solve two-center band transport equations by numerical algorithm. The effects of recording and sensitizing intensities, dopant concentration of Ce and Cu, and microphysical parameters on recording performance of two-center holographic recording have been analyzed. And the characteristic of two-center recording in (Ce,Cu)∶LiNbO3 crystal has been found, that the deep center Cu plays a key role in the recording process and a strong space-charge field has been built in Cu traps, so a high diffraction efficiency and fixing efficiency can be achieved. Numerical results have been verified by experiments. The highest saturation and fixing diffraction efficiencies achieved are 60.5% and 53.8%, respectively.