The laser coupling effect of material is a fundamental factor to influence laser interaction with matter. The coupling coefficient, which is the material absorptance of the input laser energy, depends on the surface conditions of materials, such as temperature, incident angle, surface airflow, oxidizing environment, and so on. To measure the laser coupling characteristics of materials, two typical online measuring apparatuses were developed in our laboratory. One is based on a conjugated hemi-ellipsoidal reflectometer, which is suitable to measure the laser coupling coefficients of different temperature in vacuum and air environments. The other is based on an integrating sphere and a simple airflow simulator, which can be applied to online measure the laser absorptance of materials subjected to surface airflow. The laser coupling effects on two types of structural materials, which are alloy steels and composite materials, are given in this paper. With the conjugated ellipsoidal reflectometer, the laser coupling effects on a typical alloy steel are investigated in different temperatures under the vacuum and air environment, and the experimental results are analyzed. According the results, metal oxidization plays a key role in the laser coupling enhancement effects. Especially, when the metal is subjected to high power laser irradiation in the high subsonic airflow, metal oxidization which is an exothermic reaction enhances the laser damage effect and the convective heat loss is negligible. Finally, the laser coupling effects on a typical composite material subjected to airflow are studied by using the integrating sphere with an airflow simulator, and the experimental results of laser absorptance during the laser ablation are presented.