The present invention relates to a process and a device for chlorine-free shrinkproof treatment of a wool raw material and an article thereof. In particular, the process of the present invention comprises the steps of a chlorine-free shrinkproof treatment, washing with water, protease inactivation, a softening treatment, dehydration, drying and the like, wherein a chlorine-free catalysis system consisting of a protease, a specific organic phosphine compound and the like is selected, removing the scale layer on the surface of wool fibres cooperatively and efficiently and modifying the scale layer so as to improve the shrinkproof performance of wool articles. The process of the present invention can completely replace the chloridisation shrinkproof method in the prior art, and is not only environmentally friendly, but also has low requirements for equipment, can be operated continuously and is suitable for large-scale industrial production.