Primary teeth play a crucial role in a child’s overall oral and general health. Parental awareness and knowledge have a significant influence on children’s oral hygiene behaviors and outcomes. This study aimed to assess the level of parental knowledge and awareness regarding the importance of primary teeth and oral health practices. A cross-sectional questionnaire-based survey was conducted among 350 Libyan parents attending a pediatric dental clinic. The questionnaire included items on oral hygiene practices, dietary habits, and knowledge related to primary teeth and preventive care. Data were analyzed using descriptive statistics. The majority of parents (93.4%) acknowledged the importance of primary teeth, and 91.5% agreed that children need assistance with brushing until the age of six. Additionally, 77.4% reported limiting candy intake, and 84.0% limited soft drink consumption. However, 48.1% recognized the importance of dental floss, and 64.2% were aware of the fluoride content in children’s toothpaste. Most parents (98.1%) are aware of the correct frequency for toothbrush replacement, and 75.5% are also aware of the recommended dental visit intervals. While general awareness among parents is high, specific gaps remain, particularly regarding the use of dental floss and fluoride knowledge. Targeted educational programs and collaboration between dental professionals and pediatric services are essential to improve parental oral health literacy and promote better oral health outcomes in children.