Polyurethane foams are well-known optimal thermal-insulating materials, which have good thermal insulation performance, high strength, and lightweight properties. Here, we describe a chlorine-free and fluorine-free polyurethane chemical foaming agent (CFA-1) that can react with isocyanate to release CO₂ gas and foam polyurethane. We systematically studied its application performance in the field of polyurethane spraying by substituting the current most advanced and environment-friendly physical foaming agent 1-chloro-3,3,3-trifluoroprop-1-ene in different proportions. The results show that highly competitive mechanical properties lead to economical, environment-friendly, and efficient features. The lower thermal conductivity, more compact and smaller bubble structure, and excellent compression strength were achieved by tuning the proportion of CFA-1 from 20% to 60%. Thus, a promising material system was established for the development of the rigid polyurethane foam industry.