Aggregation-induced emission (AIE)-based probes for biomolecules have gained much attention due to their fluorescence properties including turn-on type chemosensing and high quantum yield. We herein developed cationic and anionic tetraazacyclophane tetraphenylethylene conjugates 1 and 2, respectively, as a new class of AIE-based probe, and evaluated their sensing ability toward calf thymus DNA (ctDNA) and proteins (BSA, HSA, lysozyme, and trypsin). Cationic 1 responded to ctDNA with high sensitivity. In contrast, anionic 2 showed strong AIE in the presence of BSA and HSA.