The phase composition and elemental distribution of the tungsten-bearing goethite in Dabaoshan, Guangdong Province, China, were explored through various analytical methods, aiming to reveal the occurrence state and embedding characteristics of critical metal W in the ore. X-ray fluorescence analysis (XRF), powder X-ray diffraction (powder XRD), and scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS) results show that the grade of critical metal W is 1.35%, and its main minerals are tungsten-bearing goethite and quartz. Micro-area XRD and mineral liberation analyzer (MLA) results indicate that ferrotungsten ore ((W,Fe)(O,OH)₃), the tungsten-bearing phase, was mainly present in the form of stripped and banded goethite. The valuable element distribution in major minerals was also quantitatively determined. Moreover, a possible mechanism for the evolution and formation of tungsten-bearing goethite weathering was discussed, and a combined flowsheet of beneficiation–metallurgical separation was proposed to provide a theoretical basis for the high-efficient recovery of critical metal W from tungsten-bearing goethite.