Here we report a general methodology to attain novel hierarchical nanostructures using new polymer scaffolds that self-assemble to form cholesteric ID photonic mesophases existing in conjunction with microphase segregated domains. To achieve this, a series of liquid-crystalline random brush copolymers (LCRBC) consisting of cholesteryl liquid crystalline (LC) mesogen and brushlike PEG as side chain functionality are synthesized. At room temperature, all LCRBCs exhibits microphase segregation of PEG side chains on length scale of 10-15 nm, whereas LC domain forms smectic mesophase (3-7 rim LC layers). Interestingly, upon heating a cholesteric mesophase is exclusively observed for copolymer containing 78 and 85 wt % of LC content (LCRBC78 and LCRBC85, respectively) existing along with microphase segregated PEG domains. Moreover, the phase behavior of these copolymers studied by temperature controlled small angle X-ray scattering (SAXS) suggests the order disorder transition for the microphase, segregated structure coincides with the cholesteric isotropic transition. Remarkably, LCRBC78 and LCRBC85 quenched from cholesteric mesophase exhibits nanoscale hierarchical order consisting of (1) smectic LC ordering with 3-7 nm periodicity, (2) microphase segregation of PEG side chain on 10-12 nm length scale, and (3) periodicities from helical mesophase (cholesteric phase) on optical length scales of 150-200 nm. Thus, by exploiting LCRBC molecular architecture and composition, hierarchical nanostructure can be obtained and preserved which allows for the creation of unique 1D-photonic materials.