A facile and green route to fabricate sustainable and biodegradable tridimensional interconnected hierarchically meso- and macroporous polylactide (PLA) monoliths was developed. The tunable morphologies and controllable pore sizes of the monoliths based on the stereocomplex (sc) crystallization of poly(L-lactide)(PLLA) and poly(D-lactide)(PDLA) during melt blending process, were caused by the macro- and microphase separation between PLA and poly(ethylene oxide) (PEO). The proposed approach can be easily scaled-up and is environmentally sustainable, and it involves neither any toxic chemical reagents nor templates. The hierarchical morphologies of the porous materials contain mesopores regulated by the sc crystallite network formed during melt processing and macropores induced by macrophase separation. The porous structure was influenced by PDLA contents seriously, and the construction of interconnected pores made up of sc crystallite tridimensional network appears at a low PEO content of 20 wt%. The porous polymer monolith featured very good hydrophobicity with a water contact angle over 135° as well as the strong lipophilicity, endowing the materials with potential applications in selective oil-water separation. Moreover, the much higher thermal and chemical resistance of the porous PLA monoliths based on sc crystallite network allowed to significantly broaden the applications of the adsorbent in some harsh conditions and catalytic systems, compared to those based solely on PLLA.