The duration of the hypercrosslinking reaction has been used to control the extent of small pores formation in polymer‐based monolithic stationary phases. Segments of five columns hypercrosslinked for 30–360 min were coupled via zero‐volume unions to prepare columns with segmented porosity gradients. The steepness of the porosity gradient affected column efficiency, mass transfer resistance, and separation of both small‐molecule alkylbenzenes and high‐molar‐mass polystyrene standards. In addition, the segmented column with the steepest porosity gradient was prepared as a single column with a continuous porosity gradient. The steepness of porosity gradient in this type column was tuned. Compared to a completely hypercrosslinked column, the column with the shallower gradient produced comparable size‐exclusion separation of polystyrene standards but allowed higher column permeability. The completely hypercrosslinked column and the column with porosity gradient were successfully coupled in online two‐dimensional liquid chromatography of polymers.