We show that uniaxial color centers in silicon carbide with hexagonal lattice structure can be used to measure not only the strength but also the polar angle of the external magnetic field with respect to the defect axis with high precision. The method is based on the optical detection of multiple spin resonances in the silicon vacancy defect with quadruplet ground state. We achieve a perfect agreement between the experimental and calculated spin resonance spectra without any fitting parameters, providing angle resolution of a few degrees in the magnetic field range up to several millitesla. Our approach is suitable for ensembles as well as for single spin-3/2 color centers, allowing for vector magnetometry on the nanoscale at ambient conditions. PACS numbers: 76.30. Mi, 71.70.Ej, 76.70.Hb, 61.72.jd Optically addressable atomic-scale spin centers constitute the basis for nanomagnetometry with high sensitivity and high spatial resolution [1,2]. The most prominent example is the nitrogen-vacancy (NV) defect in diamond and several benchmark experiments have been performed using this system [3][4][5], including proton nuclear magnetic resonance on the nanometer scale [6,7]. The principle of magnetometry with spin-carrying color centers is based on optical detection of magnetic resonance (ODMR), subject to external magnetic field. In case of individual NV defects with spin S = 1, the projection of the magnetic field on the defect axis is measured. The NV defect in the diamond cubic lattice is oriented along one out of four 111 crystallographic axes and, therefore, using ensemble experiments the magnetic field vector B can be reconstructed [8,9]. Ensembles of the NV defects are also suggested for the implementation of high precision magnetic field sensors with femtotesla sensitivity [10,11] and solid-state frequency standards [12]. These implementations require high homogeneity of the NV centers. The NV defects can be fabricated with preferential alignment [13,14], and using nonlinear shift of the ODMR lines in relatively high magnetic fields of several tens of millitesla the transverse field component can be reconstructed [15]. However, in many demanding applications much lower magnetic fields should be detected, and the information on the magnetic field orientation is difficult to extract in this approach.Here, we demonstrate an alternative approach to implement vector magnetometry for magnetic fields below several millitesla, which is suitable for ensemble as well as for individual uniaxial spin centers with S = 3/2 [16]. As a model system, we consider a silicon vacancy (V Si ) in silicon carbide (SiC) [17][18][19][20]. Due to the polymorphism of SiC, there is a large variety of vacancy-related defects with appealing quantum properties [16,[21][22][23][24][25][26][27][28][29][30][31][32][33]. All experiments presented here have been performed at room temperature on a 4H-SiC bulk crystal, possessing hexagonal lattice structure. The crystal has been grown by the standard sublimation technique, such that the [0001]...