The paper will contain two main parts: (1) brief historical desccription on how the concept of solvation of cordination compounds evolved from the ‗clathrate’ (early 1950ths) to ‗organic zeolite’ [1] (1070ths), with a short explanations of practical ues of the formation processes, and (2) selected examples of recently investigated structures of transition metal complexes solvated in the two-phase systems (water/organic). Fantastic progress in the field of porous structures has led to generation of Metal Organic Frameworks which are amazing systems providing excellent possibilities to solvate/desolvate coordination complexes in the solid state [2]. One of the important factors influencing supramolecular solvation is associated with the physicochemical conditions of formation. When water is the solvating species then pH and ionic environment play a role. Water aggregates in the products investigated show a variety of supramolecular structures – this effect will be shortly illustrated in the paper. Organic solvates demonstrate interesting order/disorder effects as a function of temperature. This phenomenon will be illustrated with the use of novel, yet unpublished Werner ‗clathrates‘. Acetylacetonate complexes in the solvated form will be another part of the example series. One of the intriguing, novel trends is complexation of metal ions with the use of weakly coordinating molecular species which are otherwise valuable factprs leading to porous structures. Cyclodextrins are a good example of this direction [3], brief information on this subject will be given as well and a few examples from our studies will be presented in terms of solvation/molecular inclusion competitive processes.