Although phase relations in the Na2O-CaO-SiO2 system are vital to melting and thermal treatments in glass and glass-ceramics industries, the available data for thermodynamic modeling are mostly based on reports published in 1920s and 1950s. The present investigation verifies the formation of solid solutions of Na2CaSiO4 and Na2Ca2Si2O7 which have previously assumed to be stoichiometric compounds. The impact of these solid solutions on the features of the phase diagram were investigated using the equilibration-quenching-EDS/EPMA technique. The data were reported as liquidus projections and in isothermal sections within the temperature range of 1000 and 1400 °C. Ten primary phase fields were identified, namely SiO2, Na2Ca3Si6O16, combeite, Na4CaSi3O9ss, CaSiO3, Na2CaSiO4ss, Na2Ca2Si2O7ss, Na2Ca6Si4O15, Ca3Si2O7 and Ca2SiO4. In addition, some novel liquidus data and invariants points were examined in more detail. The fundamental data obtained can be employed for the thermodynamic reassessment of the Na2O-CaO-SiO2 system. The present study also discusses the findings and their impact on melting and annealing processes during the manufacture of glass and glass-ceramics.