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This contribution considers formation of interpolyelectrolyte complexes (IPECs) in organic media of low polarity (chloroform) and their properties. As anionic polyelectrolytes, linear and star-shaped poly(acrylic acid) (PAA or (PAA)N with N representing the number of arms, N = 5, 8, and 21, DPn(arm) = 100) were taken. As cationic polyelectrolytes, linear poly-4-vinylpyridines exhaustively quaternized with ethylbromide (PVPEtBr, DPw = 600, 3000) were used. Hexadecyltrimethylammonium bromide (HDTMABr) and sodium dodecylsulfate (DDSNa) were chosen to transform the corresponding polyelectrolytes into their modified forms soluble in organic media of low polarity, viz. PA•HDTMA or (PA•HDTMA)N and PVPEt•DDS, that is, via exchange of protons or low molecular weight counterions by the corresponding surfactant counterions. In the excess of PA•HDTMA or (PA•HDTMA)N, IPECs insoluble in organic media of low polarity were formed, their stoichiometry was shown to be about 1:1. In the excess of PVPEt•DDS, the formation of IPECs soluble in organic media of low polarity was observed, they apparently represent novel macromolecular architectures of "core-shell" type with a core assembled from the oppositely charged fragments of the polymeric components and a corona built up from fragments (loops and/or tails) of PVPEt•DDS incorporated in such macromolecular micelles in a certain excess.