Accurately distinguishing between enantiomeric molecules is a fundamental challenge in the field of chemistry. However, there is still significant room for improvement in both the enantiomeric selectivity (KR(S)/KS(R)) and binding strength of most reported macrocyclic chiral receptors to meet the demands of practical application scenarios. Herein, we synthesized a water‐soluble conjugated tubular host—namely, corral4BINOL—using a chiral 1,1′‐bi‐2‐naphthol (BINOL) derivative as the repeating unit. The conjugated chiral backbone endows corral4BINOL with good fluorescent emission (QY=34 % ) and circularly polarized luminescence (|glum| up to 1.4×10−3) in water. Notably, corral4BINOL exhibits high recognition affinity up to 8.6×1010 M−1 towards achiral guests in water, and manifested excellent enantioselectivity up to 18.7 towards chiral substrates, both of which represent the highest values observed among chiral macrocycles in aqueous solution. The ultrastrong binding strength, outstanding enantioselectivity, and facile accessibility, together with the superior fluorescent and chiroptical properties, endow corral4BINOL with great potential for a wide range of applications. A pair of water‐soluble enantiomeric macrocycles was prepared using a chiral 1,1′‐bi‐2‐naphthol derivative as the building unit. The conjugated backbone results in the macrocycles having attractive chiral emissive properties, exceptional recognition affinity (up to 1010 M−1) and excellent enantioselectivity (up to 18.7) in water.