An innovative [Cu(Hadp)2(Bimb)]n (KA@CP-S3) coordination polymer expands its dimensionality from a 1D chain to a 2D network. The topological analysis reveals that KA@CP-S3 has 2-connected uninodal 2D 2C1 topology. KA@CP-S3 has capable luminescent sensing for volatile organic compounds (VOCs), nitroaromatics, heavy metal ions, anions, disposed antibiotics (nitrofurantoin and tetracycline) and biomarkers. Intriguingly, KA@CP-S3 exhibits outstanding selective quenching of about 90.7% and 90.5% for the 125 mg dl-1 and 150 mg dl-1 strengths of sucrose, respectively, in aqueous solution along with other ranges in between. The photocatalytic degradation efficiency of KA@CP-S3 for the potentially harmful organic dye Bromophenol Blue displays 95.4%, which is the highest among the 13 dyes that were evaluated.