The band-A emission (around 2.8 eV) observed in high quality (device-grade) homoepitaxial diamond films grown by microwave-plasma chemical vapor deposition (CVD) was studied by means of scanning cathodoluminescence spectroscopy and high-resolution transmission electron microscopy. Recent progress in our study on homoepitaxial diamond films was obtained through the low CH4/H2 conditions by CVD. These showed atomically flat surfaces and the excitonic emission at room temperature, while the band-A emission (2.95 eV) decreased. Using these samples, we found that the band-A emission only appeared at unepitaxial crystallites (UC) sites, while other flat surface parts still showed the excitonic emission. High-resolution transmission electron microscopy revealed that there were grain boundaries which contained π-bonds in UC. This indicates that one of the origin of the band-A emission in diamond films is attributed to π bonds of grain boundaries.