We studied the influence of microstructure on the chromatographic behavior of gradient copolymers with different gradient strengths and block copolymer with completely segregated blocks by using gradient liquid adsorption chromatography (gLAC) and liquid chromatography at critical conditions (LCCC) for one of the copolymer constituents. The copolymers consist of repeating units of poly(propylene oxide) and poly(propylene phthalate) and have comparable average chemical composition and molar mass, and a narrow molar mass distribution to avoid as much as possible the influence of these parameters on the elution behavior of the copolymers. On both reversed stationary phases, the elution volume of gradient copolymers increases with the increasing strength of the gradient. The results indicate that for both modes of liquid interaction chromatography, it is important to consider the effect of microstructure on the elution behavior of the gradient copolymers in addition to the copolymer chemical composition and molar mass in the case of gLAC and the length of the chromatographically visible copolymer constituent in the case of LCCC.