In continuation of our program to discover natural product-based pesticidal agents, a series of new quinolinomatrine derivatives were prepared. Especially three-dimensional structures of five compounds were unambiguously determined by single-crystal X-ray diffraction. Among them, 21-chloroquinolinomatrine exhibited good insecticidal and acaricidal activities against two crop-threatening insect pests, Mythimna separata and Tetranychus annabaricins. Their structure-activity relationships were also discussed. (C) 2018 E(C)sevier Ltd. All rights reserved.