In this paper a simple protocol is described for estimating of solid-phase extraction (SPE) elution volumes of steroids based on retention data generated from micro-planar chromatography. Particularly, the retention of selected steroids, including estrogens and progestagens, was studied on wettable with water octadecylsilica HPTLC plates and mobile phases composed of methanol:water mixtures ranging from 20 to 100% (v/v). It was found that TLC retention data can be linearized by plotting R_M values of steroids against a reciprocal form of the organic modifier molar fraction (1/X_s). Using such a mathematical approach, the retention parameter of steroids investigated could be easily back-calculated for a wide range of mobile-phase compositions, using few initial experimental data points. The hold-up time of SPE cartridges filled with 0.5 g of C-18 adsorbent was determined experimentally, and appropriate retention factor values (k_SPE) for components of interest studied were calculated. Using an appropriate slope and intercept coefficients of the linear-regression equation formed as log k_SPE = aR_M + b, the steroids SPE elution volumes were predicted beyond the experimental data range that was available for a solid-phase extraction experiment, particularly for mobile phases that contained a high level of water.