The point spread function (PSF) effect exists ubiquitously in real remotely sensed data and such that the observed pixel signal is not only determined by the land cover within its own spatial coverage but also by that within neighboring pixels. The PSF, thus, imposes a fundamental limit on the amount of information captured in remotely sensed images and it introduces great uncertainty in the widely applied, inverse goal of spectral unmxing. Until now, spectral unmixing has erroneously been performed by assuming that the pixel signal is affected only by the land cover within the pixel, that is, ignoring the PSF. In this paper, a new method is proposed to account for the PSF effect within spectral unmxing to produce more accurate predictions of land cover proportions. Based on the mechanism of the PSF effect, the mathematical relation between the coarse proportion and sub-pixel proportions in a local window was deduced. Area-to-point kriging (ATPK) was then proposed to find a solution for the inverse prediction problem of estimating the sub-pixel proportions from the original coarse proportions. The sub-pixel proportions were finally upscaled using an ideal square wave response to produce the enhanced proportions. The effectiveness of the proposed method was demonstrated using two datasets. The proposed method has great potential for wide application since spectral unmixing is an extremely common approach in remote sensing.