Molecular organization of donor and acceptor chromophores in self-assembled materials is of paramount interest in the field of photovoltaics or mimicry of natural light-harvesting systems. With this in mind, a redox-active porous interpenetrated metal-organic framework (MOF), {[Cd(bpdc)(bpNDI)]·4.5 H2O·MF}n (1) has been constructed from a mixed chromophoric system. The μ-oxo-bridged secondary building unit, {Cd2(μ-OCO)2}, guides the parallel alignment of bpNDI (N,N′-di(4-pyridyl)-1,4,5,8-naphthalenediimide) acceptor linkers, which are tethered with bpdc (bpdcH2=4,4′-biphenyldicarboxylic acid) linkers of another entangled net in the framework, resulting in photochromic behaviour through inter-net electron transfer. Encapsulation of electron-donating aromatic molecules in the electron-deficient channels of 1 leads to a perfect donor-acceptor co-facial organization, resulting in long-lived charge-separated states of bpNDI. Furthermore, 1 and guest encapsulated species are characterised through electrochemical studies for understanding of their redox properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.