Objectives: The use of non-adhesive gel-like embolic materials (NAGLEMs) in the endovascular treatment of hypervascularized formations in the head and neck is gaining in popularity because of a number of important characteristics involved. Their primary benefits are their capacity to penetrate diseased vasculature, effectively distribute, and, most importantly, remain controllable during the process. We reviewed the literature and evaluated the results of using NAGLEMs in comparison to other embolizing substances (namely, coils, glue, and particles) as alternative embolizing agents for patients receiving care at our clinic. The process comprised evaluating the safety, effectiveness, and technological elements of endovascular therapy used to treat two categories of hypervascular pathological abnormalities that were surgically corrected between 2015 and 2023. Arteriovenous malformations (AVMs) located in the head, neck, and paragangliomas with jugular/carotid body localization are combined by intense shunting blood flow and shared requirements for the embolic agent used in endovascular treatment (such as penetration, distribution, delayed polymerization, and controllability). An analysis of the literature was also conducted. Results showed 18 patients diagnosed with neck paragangliomas of the carotid body and jugular type. Five patients with arteriovenous malformation (AVM) of the face and neck were included, consisting of sixteen females and seven males with an average age of 55 ± 13 years. Endovascular procedures were performed using NAGLEMs (ONYX (Medtronic, Irvine, CA, USA), SQUID (Balt, Montmorency, France), and PHIL (Microvention, Tustin, CA, USA)) and dimethyl sulfoxide (DMSO)-compatible balloon catheters. All patients achieved complete or partial embolization of hypervascularized formations using one or more stages of endovascular treatment. Additionally, three AVMs of the face and two paragangliomas of the neck were surgically excised following embolization. In other instances, formations were not deemed necessary to be removed. The patients’ condition upon discharge was assessed by the modified Rankin Scale (mRs) and rated between 0 and 2. Conclusion: Currently, NAGLEMs are predominantly used to treat hypervascularized formations in the neck and head due to their fundamental properties. These properties include a lack of adhesion and a delay in predictable polymerization (after 30–40 min). NAGLEMs also exhibit excellent distribution and penetration throughout the vascular bed of the formation. Adequate controllability of the process is largely achieved through the presence of embolism forms of different viscosity, as well as excellent X-ray visualization.