Among multivariate Metal-Organic Frameworks, multivariate modulated (MTVM) MOFs offer the possibility of introducing multiple functionalised units into the MOFs as defect-compensating ligands promoting porosity among other defect-related properties. However, there are no studies that rationalise the incorporation of multiple functionalised modulators and their resultant properties, hindering their molecular design and multi-applicability. In this manuscript, we introduce up to five functionalised modulators bearing NO2, F, tBu, OH and NH2 units in significant quantities (up to ca. 31 mol%) into the Ti heterometallic MOF MUV-10 in one-pot synthesis, increasing the porosity up to ca. 1.3-fold in comparison with the pristine material. We have rationalised the incorporation ratios of the different combinations of modulators among other properties. As a proof-of-concept, we have shown that there is up to a 1.7-fold enhancement in the catalytic activity of MTVM MOFs for the regioselective opening of epoxides, anticipating that this protocol can be used to produce multi-functionalised materials with a wide range of applications.