Introduction Electronic cigarette (e-cigarette) use has risen markedly worldwide in recent years, raising public health concerns. E-cigarettes contain many addictive and dangerous substances, including nicotine, different flavorings, propylene glycol, vegetable glycerin, and others, making them more appealing but, at the same time, have various harmful effects on health. The available literature on e-cigarette and vape use and their adverse effects is insufficient and limited, even in developed countries, let alone in developing nations like Pakistan. This study investigates the knowledge and attitudes of the Khyber Pakhtunkhwa (KPK) population toward e-cigarette use and its adverse effects on human health. This study also disclosed the use of e-cigarettes among different age groups, genders, and socioeconomic classes. Materials and methods A cross-sectional survey was carried out from October to December 2023 after obtaining ethical approval from the Institutional Research and Ethical Review Board (IREB). The sample size of our study was 385, which was determined using Cochran's formula. Using non-probability convenience sampling, we collected data from 403 individuals. A pre-validated questionnaire from a study conducted in Karachi was adopted for our study, which had four sections. The first section dealt with demographics, the second with knowledge of using e-cigarettes, and the third and fourth with attitudes and practices around using e-cigarettes, respectively. The chi-square test was used to compare the knowledge, attitudes, and practices (KAP) of e-cigarette users with gender and level of schooling. To assess the socioeconomic status of the participants and ascertain the percentage of e-cigarette users in each socioeconomic class, we also utilized the Kuppuswamy scale, which has been authorized for use in Pakistan. Results Of those surveyed, the majority (n=340, 84.4%) knew what e-cigarettes were. Although most respondents (n=228, 56.6%) knew about the various compounds and ingredients in e-cigarettes, they had little idea about the different amounts of nicotine in them. The majority of both men and women were aware of what e-cigarettes were and the various ingredients they included; however, women learned about e-cigarettes from the Internet, and men from friends. Regarding education, a greater percentage of intermediate and bachelor's degree holders knew what an e-cigarette was and what its various parts and ingredients were. The vast majority of participants (n=216, 53.6%) expressed that they "definitely will not" try e-cigarettes, even if a close friend were to ask them to, and they did not believe they would even if their guardian approved. Most participants (n=379, 94%) would not recommend or encourage the usage of e-cigarettes. Only 38 (9.4%) participants in our study acknowledged using e-cigarettes. Conclusion This study assessed public knowledge and attitudes toward e-cigarette use. Most individuals lacked adequate knowledge, reflected in their general disapproval. Views were similar across genders, but most users were young adults from higher socioeconomic backgrounds, likely due to greater exposure to marketing and cultural norms. As the first study of its kind in Khyber Pakhtunkhwa, it highlights the need for public education and targeted regulation. Future research should explore the role of e-cigarettes in smoking cessation, usage patterns across demographics, and the impact of marketing on youth.