Developing discotic columnar liquid crystals (LCs) with both high electrical conductivity and strong luminescence remains a challenge because the intracolumnar interdisc π-π stacking usually in ordered discotic columnar LCs is essential to generate charge transport pathways but normally detrimental to light emissions. We here present tricyanotristyrylbenzene-based quasi-discotic LCs upon bearing three wedge-shaped alkyl tails for addressing this issue. The resulted columnar materials displayed both high electrical conductivity and strong luminescence, especially for the ones stabilized by multivalent hydrogen-bonding interactions. Besides, an interesting thermochromic luminescence tuning behavior in a smooth manner was observed over a wide wavelength range for the hydrogen bond-stabilized columnar LCs. This study will lead to the future design and application of new multifunctional optoelectronic materials by integrating excellent conductivity and luminescence tuning behaviors.