High-resolution laser spectroscopy was performed on 206 Fr with the collinear resonance ionization spectroscopy (CRIS) experiment at CERN-ISOLDE. The hyperfine structure and isotope shift of the ground, first isomeric and second isomeric states were measured. The hyperfine components were unambiguously assigned to each nuclear state by means of laser-assisted nuclear decay spectroscopy. The branching ratios in the α decay of 206 Fr and 202 At were also measured for the first time with isomerically purified beams. The extracted hindrance factors allow determination of the spin of the ground, first isomeric, and second isomeric states in 202 At and 198 Bi.