The development of quantum technologies requires a thorough understanding of systems possessing quantum effects that can ultimately be manipulated. In the field of molecular magnetism, one of the main challenges is to measure high-order ligand field parameters, which play an essential role in the relaxation properties of SMMs. The development of highly advanced theoretical calculations has allowed the ab-initio determination of such parameters; however, currently, there is a lack of quantitative assessment of how good the ab-initio parameters are. In our quest for technologies that can allow the extraction of such elusive parameters, we develop an experimental technique that combines the EPR spectroscopy and µSQUID magnetometry. We demonstrate the power of the technique by performing EPR-µSQUID measurement of a magnetically diluted single crystal of Et4N[GdPc2], by sweeping the magnetic field and applying a range of multifrequency microwave pulses. As a result, we were able to directly determine the high-order ligand field parameters of the system, enabling us to test theoretical predictions made by state-of-the-art ab-initio methods.