There are described problems concerning chromatographic separation and determination of mono-, di-, tri-, tetra- and hexabenzyl derivatives of germanium in the paper. Investigations were taken, considering confirmed modification of stationary phase (silica gel) by chlorobenzylgermanium compounds in usual chromatographic process. The investigations were based on Nuclear Magnetic Resonance techniques (13C CP/MAS NMR, 29Si CP/MAS NMR), infrared spectroscopy with Fourier transform (FTIR) and imaging by means of scanning electronic microscope (SEM). Mentioned techniques allowed to characterize adsorbent surface on a molecular level and to confirm unambiguously the participation of benzylgermanium derivatives in the process of modification of stationary phase surface. Taking into consideration the interaction of analyzed compounds with adsorbent, a new methodology of chromatographic separation and determination of benzylgermanium derivatives, using so-called dedicated columns, has been elaborated. From practical point of view results obtained by means of elaborated analytic procedure were evaluated and controlled according to criteria of validation.