Sixty milligrams of porous metal-organic framework (MOF) material, poly-[Cd₂(L1)], packed into a micro-pipette tip and connected with a disposable syringe pump was demonstrated for suitability as solid-phase extraction media. This novel material offered a portable platform for small scale separation, and was used here for mixtures of polyaromatic hydrocarbons (PAHs) and polar compounds, employing a hexane/ethyl acetate mobile phase elution system. Sequential aliquots of 30 μL eluate collected from the tips were analysed by using gas chromatography (GC) coupled with flame ionisation detection, to illustrate the molecular fractionation of multicomponent mixtures. Plots of (tip elution volume)_˟(GC retention) were generated and analysed based on hydrophobic elution from the MOF, and retention order in GC separation; GC retention was confirmed by using GC hyphenated with quadrupole mass spectrometry. Beside some completely resolved compounds eluted from the MOF material, increased retention factors were observed for linear PAH structures of four or more rings depending on the analyte dimension. MOF with larger pores also provided stronger interaction towards PAHs with six rings. For polar compound separation, although higher retention volume from the tip was observed for more polar compounds according to their dipole moment, bisphenol A and 4,4'-biphenol showed greater retention volumes than the expected trend, due to the additional interaction provided by the ligand. Those MOFs reveal multi-separation mechanisms of size, polarity and ligand-analyte interactions.