The spectrum and electro-optic properties of CdSe quantum dots are studied. Spectrum wavelength shifts that are due to the quantum size effect and to the electro-optic Stark effect are investigated. It is found that CdSe quantum dot-polymer composites formed by an electrostatic self-assembly (ESA) technique exhibit high internal electric fields. Using the second-order perturbation theory of the ls-ls energy shift (Stark effect), we estimate the internal field of the ESA film to be as high as 2.6 X 10(8) V/m. This value results in a much higher absorption coefficient and electro-optic coefficients for ESA films than for their bulk crystal counterparts or for spin-coated film samples. The relationships among unusual spectra, film structure, and high electro-optic response are analyzed. These results are useful both for understanding the physical mechanisms of semiconductor quantum dots and for developing high-performance photonic devices. (c) 2005 Optical Society of America.