Polyphenylene sulfide (PPS) is an engineering plastic; when reinforced with fillers, it exhibits high heat resistance, strength, and molding/dimensional stability. Plating on PPS without using harmful chemicals can meet the following requirements due to its excellent properties: low environmental load process, lightweight metal substitute materials, electromagnetic wave shielding materials, etc. This study focused on metallizing by atmospheric ultraviolet (UV) treatment of PPS. This process is generally used for the pretreatment of painting and adhesion, and it entails a small environmental load; however, the UV treatment of moist air produces various chemical species. Therefore, the humidity effect during metallizing via atmospheric UV treatment was investigated, revealing its influence on the adhesion strength of the resulting metal film. In a dry environment, a metal film with strong adhesion can be formed on PPS, and UV treatment under such conditions can maintain the structure of the PPS surface. In contrast, a weak layer was generated under wet conditions, reducing the adhesion strength between the metal film and PPS.