Halogen bonding is an efficient tool for self-assembling haloperfluorocarbons (PFC) and hydrocarbons (HC) [1]. Its particular ability to control spontaneous resolution in hybrid PFC-HC systems has been discovered only recently [2]. Up to now we observed spontaneous resolutions in four cases affording chiral cocrystals, space group P212121. Three of them involved long-chain iodo-PFC?s (C8-C10) with either QUATS or N,N,N?,N?-tetramethyl-pphenylendiamine as bases. Their different features with regard to the segregation behaviour and the conformation of the PFC chains will be outlined. The X-ray structure of a chiral alkali halide complex 1 (Figure) involving a tripodand will also be presented.