This study established the connection in turbulent boundary layers between the first two dominant proper orthogonal decomposition (POD) modes and the instantaneous large-scale turbulence structures. The velocity fields consistent with the signature velocity fields of the hairpin vortex packets in two-dimensional PIV (particle image velocimetry) measurement planes are observed as the major contributors to the first two POD modes. Another kind of equally important turbulence structure is the large region of Q4 vectors, which may possibly be obtained by slicing the outskirts of the three-dimensional structure of the hairpin vortex packet by PIV planes. The streamwise Reynolds normal stress, Reynolds shear stress, and the length scales of the two-point velocity correlation coefficients ρ uu and ρ uv are noticeably decreased without those large-scale turbulence structures contributing significantly to the first POD mode. Similarity of these results is observed at a higher Reynolds number.