Attempting to derive a high-throughput computational workflow to expedite the discovery of cis-Pd2L2L'2 heteroleptic MOCs, a combined experimental and computational study was undertaken. Based on the well-known geometric complementarity approach, two sets of ligands (with converging and diverging coordination vectors) were examined in a combinatorial fashion for integrative self-assembly with Pd(II). Computational modelling, in the form of relatively simple geometric analyses, as well as more expensive geometry-optimisations and single-point energy calculations, were performed to post-rationalise the experimental results.