In this work, an intensity-enhanced C≡C stretching infrared (IR) absorption is observed in hexakis[(trimethylsilyl)ethynyl]benzene (HTEB), whose IR transition dipole magnitude becomes comparable to that of a typical C═O stretch, and the enhancement is believed to be due to a joint effect of π-π conjugation and hyperconjugation associated with a terminal trimethylsilyl group. Using dynamical time-dependent two-dimensional infrared (2D IR) spectroscopy, a picosecond intramolecular energy redistribution process is observed between two nondegenerate C≡C stretching modes, whose symmetry breaking is attributed to a noncovalent halogen-bonding interaction between HTEB and solvent CH2Cl2. The rigid structure of HTEB and limited structural dynamics are also inferred from the insignificant initial spectral diffusion value extracted from the 2D IR spectra. This work provides the first nonlinear infrared investigation of the conventionally weak C≡C stretch. The methods outlined are particularly important for detailed understanding of the structure-related processes such as vibrational energy transfer in novel C≡C species containing materials such as graphdiyne.