Measurements of the 2 H( 16 C, 16 C * → 4 He+ 12 Be or 6 He+ 10 Be) 2 H inelastic excitation and clusterdecay reactions have been carried out at a beam energy of about 23.5 MeV/u. A specially designed detection system, including one multi-layer silicon-strip telescope at around zero degrees, has allowed the high-efficiency three-fold coincident detection and therefore the event-by-event determination of the energy of the unstable nucleus beam. The decay paths from the 16 C resonances to various states of the final 10 Be or 12 Be nucleus are recognized thanks to the well-resolved Q-value spectra. The reconstructed resonances at 16.5(1), 17.3(2), 19.4(1) and 21.6(2) MeV are assigned as the 0 + , 2 + , 4 + and 6 + members, respectively, of the positive-parity (3/2 − π ) 2 (1/2 − σ ) 2 -bond linear-chain molecular band in 16 C, based on the angular correlation analysis for the 16.5 MeV state and the excellent agreement of decay patterns between the measurements and theoretical predictions. Moreover, another intriguing high-lying state was observed at 27.2(1) MeV which decays almost exclusively to the ∼6 MeV states of 10 Be, in line with the newly predicted pure σ-bond linear-chain configuration.