This PhD thesis proposes a bottom-up approach that accurately addresses the operational flexibility embedded in each part of a multi-energy system (MES). Several models which cover the simulations from replicating domestic electrified demands to power system scheduling are proposed. More specifically, a domes-tic multi-energy consumption model is firstly developed to simulate one minute resolution energy profiles of individual dwellings with the installation of prospec-tive technologies (i.e., electric heat pumps (EHPs), electric vehicles (EVs)). After-wards, a fast linear programming (LP) unit commitment (UC) model is devel-oped with the consideration of characteristics of generators and a full set of ancil-lary services (i.e., frequency response and reserves). More importantly, the fre-quency response requirements in low inertia systems are assessed with the con-sideration of three grid frequency regulations (i.e., rate of change of frequency, Nadir and quasi-steady state). Furthermore, the UC model has integrated vari-ous flexibility contributors in MES to provide ancillary and flexibility services, which include pumped hydro storages (PHSs), interconnectors, batteries and demand side resources (i.e., individual EHPs, heat networks, electrolysers). More importantly, the fast frequency response (FFR) provision from nonsynchronous resources is implemented and the demand response application of electrolysers is taken as an example to provide FFR in the UC model. By using the integrated UC model with the consideration of flexibility services provided by resources in the MES, the advantages of multi-energy operation can be clearly identified which can be used to inform system operators and policy makers to design and operate energy systems in a more economic and environment-friendly way.