3D inkjet printing (3DP) technology has the advantages of fast processing speed and high precision, but achieving a strong combination of "powder" and "ink" in polymer materials remains a huge challenge. In this work, thiolated polylactic acid (PLA) microspheres were prepared by amine ester reaction between cysteine and PLA in a "green" water environment. Then, thiolated PLA microspheres were used as the "powder", and acryloylmethiolane containing double bonds was used as the "ink" to simulate 3DP. With the rapid "thiol ene click" reaction, PLA scaffolds with covalent bonding interfaces can be prepared within 20 seconds. Both thiol microspheres and scaffolds exhibit good biocompatibility, with a tensile strength of up to 13.2MPa and a Young's modulus of 722MPa, meeting the performance requirements of bone tissue scaffolds. Therefore, a new strategy has been provided to solve the interface bonding problem in 3DP technology, which is beneficial for the 3DP molding of PLA powder and promotes its application in the field of life and health.