This paper reports the successful application of a self-developed, miniaturized, low-power nano-star tracker for precise attitude measurement of a 5-m-long satellite extension boom. Such extension booms are widely used in space science missions to extend and support payloads like magnetometers. The nano-star tracker, based on a CMOS image sensor, weighs 150 g (including the baffle), has a total power consumption of approximately 0.85 W, and achieves a pointing accuracy of about 5 arcseconds. It is paired with a low-cost, commercial lens and utilizes automated calibration techniques for measurement correction of the collected data. This system has been successfully applied to the precise attitude measurement of the 5-m magnetometer boom on the Chinese Advanced Space Technology Demonstration Satellite (SATech-01). Analysis of the in-orbit measurement data shows that within shadowed regions, the extension boom remains stable relative to the satellite, with a standard deviation of 30′′ (1σ). The average Euler angles for the “X-Y-Z” rotation sequence from the extension boom to the satellite are [−89.49°, 0.08°, 90.11°]. In the transition zone from shadow to sunlight, influenced by vibrations and thermal factors during satellite attitude adjustments, the maximum angular fluctuation of the extension boom relative to the satellite is approximately ±2°. These data and the accuracy of the measurements can effectively correct magnetic field vector measurements.