We introduce a new field-flow fractionation (FFF) technique, whereby molecules are separated based on their differential interaction (dielectrophoresis (DEP)) with optical electric fields, i.e. electric fields with frequencies in the visible and near-infrared range. The results show that a parallel array of axially non-uniform optical fields yielding an attractive potential (positive-DEP-FFF) is advantageous for the separation of polymers, biomolecules, and nanoparticles over very short distances. Furthermore, positive-DEP-FFF yields superior selectivity and resolution compared to conventional separation techniques, which do not lend themselves to miniaturization. A wide range of parameters are considered and the results are presented considering traditional chromatography parameters: the retention ratio and resolution. A simple analytical model is introduced which captures the trends for small normalized decay lengths and will be useful in the design of experimental separation platforms.