Pore structure of the porous polydivinylbenzene microspheres is controlled by the degreeof crosslinkage and the diluent used. It is proved by chromatographic results that the higher thedegree of crosslinkage is, the more the micellar pores will be formed, and the nature as wellas the quantity of the diluent determine the real pore structure. Among the structural para-meters of the microspheres, the size and the pore diameter affect the performance in HPLCmostly. The linear sample capacity of the microspheres in 1--2 order of magnitude larger thanthat of the Silica-ODS. According to this result, it could be confirmed that the solute mole-cules penetrate deeply into the skeleton of the polymer network. Based on the polymeric struc-ture with the same chemical composition but different in pore structure, the contribution tothe retention of several organic compounds by Henry’s and/or adsorption coefficient has beenstudied. The results obtained show that Henry’s coefficient is approximately 80% of thetotal contribution, i. e. dissolution mechanism plays the main role in the chromatographicprocess, especially in case of polar compounds. The experimental result that the chroma-tographic separation relatively slightly depends upon the sueface area of the polymer isanother ovidence. It is better to define this kind of polymeric stationary phase as a sorbentrather than an adsorbent. From the point of view of dissolution mechanism, it is suggestedthat a homogeneous porous polymeric stationary phase constructed with chemically rigid ske-letal structure and sufficiently thin bulk polymeric phase inside the microspheres should bean ideal packing for chromatography. Pore ​​structure of the porous polydivinylbenzene microspheres is controlled by the degree of crosslinkage and the diluent used. It is proved by chromatographic results that the higher thedegree of crosslinkage is, the more the micellar pores will be formed, and the nature as wellas the quantity of the Among the structural para-meters of the microspheres, the size and the pore diameter affect the performance in HPLC mostly. The linear sample capacity of the microspheres in 1--2 order of magnitude larger thant of the Silica- ODS. According to this result, it could be quite that the solute mole-cules penetrate deeply into the skeleton of the polymer network. Based on the polymeric structure-the same chemical composition but different in the pore structure, the contribution tothe retention of Several organic compounds by Henry’s and / or adsorption coefficient has been derived. The results obtained show that Henry’s coefficient is approximately 80% of the total contribution, ie dissolution mechanism plays the main role in the chromatographicprocess, especially in case of polar compounds. The experimental result that the chroma-tographic separation relatively determined depends on the sueface area of ​​the polymer isanother ovidence. It is better to define this kind of polymeric stationary phase as a sorbentrather than an adsorbent. From the point of view of dissolution mechanism, it is suggested that a homogeneous porous polymeric stationary phase constructed with a chemically rigid ske-letal structure and magnetic thin bulk polymeric phase inside the microspheres should bean ideal packing for chromatography.