Obtaining electronic and atomic structure of material simultaneously is very important for developing the nano-technology. In this paper, we demonstrate that atomic and electronic structure of an interface can be extracted with combination of Gerchberg-Saxton indirect microscopy and electron spectroscopy imaging (ESI) technique. Basically, Gerchberg-Saxton algorithm includes two projections. Projection in the real space is a maximum entropy (ME) de-convolution process and in reciprocal space is an amplitude substitution process. It has been shown that Gerchberg-Saxton algorithm can extend the structural resolution to near 0.1 nm. An application case of Gerchberg-Saxton algorithm to solve the atomic structure for 3C-polytypic SiC boundary is shown. ESI spectrum processed by FFT interpolation, maximum entropy de-convolution and wavelet transformation allow us to extract 2-dimensional map of the sp2/sp3 with a sub-nanometer resolution. Grain boundary and interface at SiC are good candidates for this study, since the bond distance of Si-C is slightly less than 0.1 nm which is not routinely resolvable using a FEG TEM and Si-L (99eV) and C-K-edges (283 eV) locate in a reasonable energy range. The resultant electronic structure can be compared with that calculated using WIEN97. An example of quantitative analysis on 2-dimensional sp3/sp2 map deduced from the C K-edge of ESI spectra acquired from 6H-SiC is given.