The complex formed between octyltrimethylammonium bromide (8TAB) and (R)-(+)-1,1'-bi-2-naphthol (RBNP) crystallizes in the monoclinic space group P2 1 with one crystallographically independent 8TAB molecule and two crystallographically independent RBNP molecules in the asymmetric unit. The crystal structure demonstrates that the nonplanar shape of the RBNP molecule affects the packing mode of the alkyl chains. The host:guest ratio as well as the length of the alkyl chain play significant roles in the packing structure of the complex. The alkyl chain does not have an all-trans fully extended conformation but one which is bent. The hydrogen bonds and C-H...pi interactions stabilize the crystal structure of the complex.