Sustainability and resilience are major challenges for the building sector in order to meet energy efficiency and low carbon emissions goals. Based on the defined and quantified targets of the EU climate change policy, Renewable Energy Systems (RESs) are among the top-priority measures for accomplishing the target of decarbonization in buildings. Nevertheless, the choice of the type of RES is not a one-dimensional problem, and the optimal combination may not be unique. The aim of this paper is the energy and environmental evaluation of renewable energy technologies with emphasis on biomass and solar thermal systems for heating applications in residential buildings. More specifically, and aiming at the maximum possible contribution of renewable energy sources in the total final energy consumption for the needs of zero energy buildings, different scenarios are presented based on a Life Cycle Energy Analysis (LCEA) approach. The methodology is based on quantifying the environmental impacts (midpoint analysis), as well as endpoint analysis, in order to define the impact on human health, ecosystem damage, and resource depletion. The LCEA has been conducted, supported by the SimaPro tool, ensuring the environmental impact assessment result. A combination of RES technologies based on solar and biomass are examined and compared to conventional fossil fuel heating systems according to technical, energy, and environmental criteria. Finally, the energy system technologies were compared in correlation to a building’s thermal insulation level. The first set of simulations fulfilled the minimum thermal insulation requirements, according to the national energy performance regulation, whilst the second set of simulations was based on increased levels of insulation. The point of this analysis was to correlate the impact of thermal insulation to RES technologies’ contribution. The results determined that the best available energy solution, focusing on technical and environmental criteria, is the combination of biomass and solar thermal systems for covering the heating processes in residential buildings. More specifically, the combined biomass–solar system has a lower overall environmental impact, due to the reduction in gaseous pollutant emissions, as well as the reduction in the amount of used fuel. The reduction in the total environmental impact amounts to a percentage of approximately 43%.