Pain is one of the most common complaints leading to a pediatric emergency department visit and is associated with various painful procedures, leading to increased anxiety and stress. Assessing and treating pain in children can be challenging, so it is crucial to investigate new methods for pain diagnosis. The review aims to summarize the literature on non-invasive salivary biomarkers, such as proteins and hormones, for pain assessment in urgent pediatric care settings. Eligible studies were those that included novel protein and hormone biomarkers in acute pain diagnostics and were not older than 10 years. Chronic pain studies were excluded. Further, articles were divided into two groups: studies in adults and studies in children (<18 years). The following characteristics were extracted and summarized: study author, enrollment date, study location, patient age, study type, number of cases and groups, as well as tested biomarkers. Salivary biomarkers, such as cortisol, salivary α-amylase, and immunoglobulins, among others, could be appropriate for children as saliva collection is painless. However, hormonal levels can differ among children in different developmental stages and with various health conditions, with no predetermined levels of saliva. Thus, further exploration of biomarkers in pain diagnostics is still necessary.