We report the second overtone (Δv=3←0) spectra of the free-HF (ν1) and bound-HF (ν2) stretches of (HF)2 using laser induced fluorescence. Subbands of K=0←0 and K=1←0 are detected near 900 nm with linewidths spanning almost two orders of magnitude. The line broadening (Δνpd) due to vibrational predissociation is not only mode specific but also is state specific. A fit of the spectral lines to a Voigt profile reveals Δνpd=10 GHz for the parallel band of 3ν2, and 0.10 and 1.9 GHz for the parallel and the perpendicular bands of 3ν1, respectively. The linewidths of these subbands are J and tunneling state independent. The K-dependent vibrational predissociation is attributed to near-resonant centrifugal interaction of the K=1 state with the K=1 combination mode of the bound HF stretch (3ν2) and the antisymmetric bend (ν5). The exceedingly state-specific behavior is at variance with elementary density of states arguments. Spectroscopic constants of these two K subbands and two tunneling states (A+ and B+) of 3ν1 are determined from their rotationally resolved manifolds. For the parallel band, we obtain band origins ν0=11 273.501 cm−1 (A+), 112 73.499 cm−1 (B+), rotational constants B̄=0.221 177 cm−1 (A+), 0.221 179 cm−1 (B+), and centrifugal distortion constants D=2.02×10−6 cm−1 (A+), 2.05×10−6 cm−1 (B+). For the perpendicular band, ν0=11 299.850 cm−1 (A+), 11 299.847 cm−1 (B+), and B̄=0.222 02 cm−1 (A+), 0.222 04 cm−1 (B+). The interconversion tunneling splitting is found to be 0.0024 cm−1, showing that the tunneling motion of the dimer could be quenched entirely. For the 3ν2 where only the R branch is resolved, the breadth of the lines prevents accurate determination of its spectroscopic constants. The band is estimated to center at 11 043.09 cm−1 with a rotational B̄ constant of 0.2240 cm−1. All the constants indicate that a stronger hydrogen bond is formed at higher valence vibrational states. The shifts of the free- and the bound-HF stretching frequencies from that of the monomer are −99.306 and −329.72 cm−1, respectively. Finally, we present an analysis for the rotational dependence of the tunneling in states of v1, which suggests that the transition state, under the assumption of C2h geometry, has the HF units oriented at 33° with respect to the F–F axis.