The ability to tune polymer monolith porosity on multiple length scales is desirable for applications in liquid separations, catalysis, and bioengineering. To this end, we have developed a facile synthetic route :to nanoporous polymer monoliths based on controlled polymerization of styrene and divinylbenzene from a poly(lactide) macro-chain transfer agent in the presence of nonreactive poly(ethylene oxide) (PEO). Simple variations in the volume fraction and/or molar mass of PEO lead to either polymerization-induced microphase separation or simultaneous macro- and microphase separation. These processes dictate the resultant morphology, and allow, for control of the macro- and microstructure of the monoliths. Subsequent selective etching produces monoliths with morphologies that can be tailored from mesoporous, with control over mesopore size, to hierarchically, meso- and macroporous, with percolating macropores. This convenient synthetic route to porous polymer monoliths has the potential to be useful in applications where both rapid mass transport and a high surface area are required.