Small-angle neutron scattering (SANS) was used to examine dilute solutions of a poly(quinoxaline-2,3-diyl) (PQX) with (R)-2-octyloxymethyl side chains in deuterated THF or a mixture of deuterated 1,1,2-TCE and THF (8/2, v/v), in which the PQX adopts pure P- and M-helical structures. The structures of the PQX that were obtained based on the SANS experiments in combination with theoretical calculations suggest that in THF, the chiral side chains of the P-helical PQX are extended, whereas in the 1,1,2-TCE/THF mixture, the side chains of the M-helical PQX are folded. Consequently, P-helical structures should be preferred in good solvents such as THF, which solvate the extended side chains, whereas M-helical structures should be preferred in poor solvents such as 1,1,2-TCE, wherein the side chains adopt shrunken conformations with maximized van der Waals interactions between the side chains. This study thus reveals the first example for fully determined nuanced conformations of the side chains of synthetic polymers in solution based on SANS experiments and theoretical calculations.