Background and objectives: Early childhood caries (ECC) is the most common chronic disease of childhood in many developing countries, which is associated with local, systemic, psychological, and social consequences. Multiple variables are shown to be associated with an increased risk of ECC. The knowledge regarding the role of saliva in the pathophysiological process of ECC still remains controversial and unexplored. Scanty studies focused on probing the role of salivary flow rate, pH, buffering capacity, and secretory immunoglobulin A (sIgA) in unstimulated whole saliva of children with ECC and children without ECC. Aim: To assess the salivary flow rate, pH, buffering capacity, and sIgA levels in children with ECC and caries-free children and to evaluate their role in caries risk assessment. Materials and Methods: The study was carried out among 64 children aged between 24 and 71 months. Clinical examinations were carried out according to the criteria by the World Health Organization, and carious status was recorded. Subjects were categorized as group I with ECC (dmfs-Decayed, Missing or Filled Surfaces (Deciduous dentition) of ≥5), and group II included children without ECC (dmfs = 0). Unstimulated whole salivary samples were collected in a sterile vial and stored at −70°C by draining. Estimations of salivary flow rate, pH, buffering capacity, and sIgA levels were done. Digital pH meters were used for the estimation of pH and buffering capacity. A human IgA enzyme-linked immunosorbent assay (ELISA) kit was used to estimate sIgA levels. Statistical software IBM Statistical Package for the Social Sciences (SPSS) statistics 20.0 (IBM Corporation, Armonk, New York, United States of America) was used to analyze the data. Results: The mean salivary flow rate decreased in group I children with ECC (0.15 ± 0.05) when compared to group II children without ECC (0.67 ± 0.14), which was statistically significant. In caries active children, no statistically significant correlation was found between salivary flow rate and the dmfs scores [r-value (−0.247)] and p-value (0.147). The mean level of salivary pH is decreased in group I children with ECC (4.65 ± 0.4) when compared to group II children without ECC (7.28 ± 0.18). In the caries active group, the levels of salivary pH decrease as the dmfs scores increase, and this correlation is found to be statistically significant (r-value of 0.547 and p-value of 0.002). The mean level of buffering capacity is decreased for caries-active children (5.45 ± 0.49) when compared to caries-free children (8.94 ± 0.42). In caries active children, as the dmfs scores increase, the salivary buffering capacity decreases, and this correlation is found to be not statistically significant (r-value of −0.334 and p-value of 0.161). The mean levels of sIgA in group I children with ECC were higher (10.61 ± 0.90) than that in group II children without ECC (6.11 ± 1.22). In the caries-active group, the salivary sIgA levels were comparatively higher than in the caries-free children. As the dmfs scores increase, the level of the sIgA increases in caries-active children, and this correlation is noted to be highly statistically significant (r-value of 0.769 and p-value 0.008). Conclusion: Children with ECC showed decreased salivary flow rate, pH, buffering capacity, and increased sIgA levels, while children without ECC showed increased salivary flow rate, pH, buffering capacity, and decreased sIgA levels. The salivary parameters, such as salivary flow rate and buffering capacity, showed no correlation with the dmfs score, while salivary pH and sIgA levels have a positive correlation in caries-active children.