We investigated, via two-dimensional heterospectral correlation analysis of wide-angle X-ray scattering (WAXS) and infrared (IR) spectroscopy, the specific chemical interactions existing in weakly interacting polystyrene-block-poly(n-pentyl methacrylate) copolymers (PS-PnPMA). PS-PnPMA was shown to exhibit a closed-loop-type phase behavior, where, upon heating, a lower disorder-to-order transition (LDOT) was found at lower temperatures, and an upper order-to-disorder transition (UODT) was observed at higher temperatures. The specific interaction between the PS and PnPMA blocks mainly arises from the dipole in the benzene ring of PS and the induced dipole in the PnPMA due to cluster formation with a size of 1 similar to 2 nm. We found that the synchronous 2D WAXS-IR heterospectral correlation spectrum of the ordered state was completely different from that in the two disordered states. The CH group of the main chains of PS and PnPMA did not contribute to the cluster formation in the two disordered states, indicating that the main chains of PS and PnPMA blocks were randomly distributed in the two disordered states. However, only the C=C group in the PS block contributed to the cluster at a disordered state below the LDOT, whereas both the C-C-O group in PnPMA and the entire phenyl ring and C=C group in PS contributed to cluster formation at another disordered state above the UODT. Thus, the probability that PS (and PnPMA) chains were located at their own neighboring chains at one disordered state above the UODT is larger than that at another disordered state below the LDOT.