The archival records of chemical composition of mineral waters in Szczawno-Zdrój spa were analyzed in terms of variation of ionic ratios to explain the possible source and origin of the major compounds dissolved in water and evolution of groundwater chemical composition in time. The analyzed data contained the longest available series of chemical records, dating back to 1962, and related to waters discharged by five main springs: Dąbrówka, Marta, Młynarz, Mieszko and Mieszko 14. The research showed that mineral waters in Szczawno-Zdrój belong to shallow meteoric CO2-rich, Rn-containing groundwaters which form their chemical composition mainly through the interaction with aquifer rocks. Detailed analysis of long-term variation of ionic ratios revealed that (1) the carbonates weathering, mostly acid hydrolysis of limestones and dolomites, and (2) the ion exchange reactions with clay minerals, mainly the so-called natural softening, play a fundamental role in formation of the chemical composition of studied waters. Both processes are responsible for the occurrence of dominant ions in solution such as Ca2+, Mg2+, Na+, and HCO3−. The aluminosilicates hydrolysis occurs with variable extent, but plays rather secondary role in formation of chemical composition. The time distributions of major element concentrations in studied waters showed a characteristic “concave” shape, indicating the decrease in concentrations beginning in the 60s and ending around 2005–2010. Such “concave” shape trends are not reflected in time distribution of ionic ratios which strongly suggests the occurrence of a simple dilution of chemical composition of mineral waters by the influx of fresh water. The observed considerable fluctuations of chemical composition of mineral waters in Szczawno-Zdrój are most probably associated with climatic factors, namely: the increased amounts of atmospheric precipitation in particular periods of time and its seasonal distribution. Such influx of fresh waters reduces considerably mineralization of shallow groundwaters and directly increases springs discharge.