Four-bilayer Ge quantum dots (QDs) with Si spacers were grown on Si(001) substrates by ultrahigh vacuum chemical vapor deposition. In three samples, all Ge QDs were grown at 520 °C, while Si spacers were grown at various temperatures (520 °C, 550 °C, and 580 °C). Enhancement and redshift of room temperature photoluminescence (PL) were observed from the samples in which Si spacers were grown at a higher temperature. The enhancement of PL is explained by higher effective electrons capturing in the larger size Ge QDs. Quantum confinement of the Ge QDs is responsible for the redshift of PL spectra. The Ge QDs' size and content were investigated by atomic force microscopy and Raman scattering measurements.