The behavior of cast Ti-6Al-4V and Ti-6Al-2Sn-4Zr-2Mo during chemical milling in hydrofluoric-nitric (HF-HNO3) acid solutions with 1:3 and 1:11 molar ratios was investigated using electrochemical and atomic force microscopy (AFM) techniques. Faster corrosion rate in 1:3 solutions was measured for Ti-6Al-4V than for Ti-6Al-2Sn-4Zr-2Mo, whereas in 1:11 solution Ti-6Al-2Sn-4Zr-2Mo exhibited higher corrosion rate. Scanning Kelvin probe force microscopy measurements revealed difference in the Volta potential between the α-laths and the β-layers in the Widmansttäten microstructure indicating operation of microgalvanic cells between the microconstituents when in contact with HF-HNO3 solution. The AFM topography measurements demonstrated faster corrosion of the α-laths compared to the β-layers, in both alloys. In 1:3 solutions, higher α/β height difference was measured in Ti-6Al-4V, whereas in 1:11 solution, the difference was higher in Ti-6Al-2Sn-4Zr-2Mo. The results revealed that the chemical milling behavior of the two investigated alloys is controlled by the microscopic corrosion behavior of the individual microconstituents.