Electron-beam-direct-write lithography has been considered a candidate next-generation technique for achieving high resolution. An accurate point spread function (PSF) is essential for reliable patterning prediction and proximity-effects correction. It can be derived via an effective parametric PSF calibration methodology, typically involving the fitting of the absorbed energy distribution (AED) from an electron-scattering simulation. However, the existing parametric PSF calibration methodology does not employ a systematic approach to obtain a new PSF form that is both compact and accurate when conventional PSF forms are not satisfactory. Only the AED fitting quality (rather than its patterning-prediction quality) is considered during the conventional calibration methodology. It also lacks a process to consider whether the predicted deviation (as simulated using the chosen PSF form) is satisfactory. This paper proposes a new parametric PSF calibration methodology to systematically obtain a PSF form consisting of the smallest number of terms, with a better combination of basis functions and that optimizes pattern accuracy. The effectiveness of using the new methodology is demonstrated in terms of fitting accuracy, patterning-prediction accuracy, and patterning sensitivity.