The rapid development of nuclear technology has brought convenience to medical, industrial, and military fields. However, long-term exposure to a radiation environment with high energy will result in irreversible damage, especially to human health. Traditional lead-based radiation protection materials are heavy, inflexible, inconvenient for applications, and could lead to toxicity hazards and environmental problems. Therefore, it has become a mainstream topic to produce high-performance shielding materials that are lightweight, flexible, and wearable. Polymer composites are less dense and have excellent flexibility and processability, drawing great interest from researchers worldwide. Many attempts have been made to blend functional particles and polymeric matrix to produce flexible and wearable protection composites. This paper presents an extensive overview of the current status of studies on lead-free polymer composites as flexible and wearable protection materials. First, novel functional particles and polymer matrices are discussed, and recent results with potential applications are summarised. In addition, novel strategies for preparing polymeric shielding materials and their respective radiation shielding properties are analyzed. Finally, directions for developing lead-free polymeric shielding materials are indicated, and it is beneficial to provide additional references for obtaining flexible, lightweight, and high-performance wearable shielding materials.