Spacecraft relative pose estimation for an uncooperative spacecraft is challenging because the target spacecraft neither provides sensor information to a chaser spacecraft nor contains markers that assist vision-based navigation. Moreover, the chaser does not have prior pose estimates when initiating the pose estimation. This paper proposes a new monocular pose estimation algorithm that addresses these issues in pose initialization situations for a known but uncooperative target spacecraft. The proposed algorithm finds convexity defect features from a target image and uses them as cues for matching feature points on the image to the points on the known target model. Based on this novel method for model matching, it estimates a pose by solving the PnP problem. Pose estimation simulations are carried out in three test scenarios, and each assesses the estimation accuracy and initialization performance by varying relative attitudes and distances. The simulation results show that the algorithm can estimate the poses of spacecraft models when a solar panel length and the number of solar panels are changed. Furthermore, a scenario considering the surface property of the spacecraft emphasizes that robust feature detection is essential for accurate pose estimation. This algorithm can be used for proximity operations with a known but uncooperative target spacecraft. Specifically, one of the main applications is relative navigation for on-orbit servicing.