Flexibility is crucial to enable the penetration of high shares of renewables in the power system while ensuring the security and affordability of the electricity dispatch. In this regard, heat–electricity sector coupling technologies are considered a promising solution for the integration of flexible devices such as thermal storage units and heat pumps. The deployment of these devices would also enable the decarbonization of the heating sector, responsible for around half of the energy consumption in the EU, of which 75% is currently supplied by fossil fuels. This paper investigates in which measure the diffusion of district heating (DH) coupled with thermal energy storage (TES) units can contribute to the overall system flexibility and to the provision of operating reserves for energy systems with high renewable penetration. The deployment of two different DH supply technologies, namely combined heat and power units (CHP) and large-scale heat pumps (P2HT), is modeled and compared in terms of performance. The case study analyzed is the future Italian energy system, which is simulated through the unit commitment and optimal dispatch model Dispa-SET. Results show that DH coupled with heat pumps and CHP units could enable both costs and emissions related to the heat–electricity sector to be reduced by up to 50%. DH systems also proved to be a promising solution to grant the flexibility and resilience of power systems with high shares of renewables by significantly reducing the curtailment of renewables and cost-optimally providing up to 15% of the total upward reserve requirements.