In　an　effort　to　develop　reactivity-based　dynamic　covalent　bonding　and　to　expand　the　scope　and　application　of　the　dynamic　covalent　chemistry,　in　situ-generated　simple　generic　iminium　ions　were　utilized　for　the　dynamic　covalent　binding　of　monoalcohols　with　high　affinity.　Hammett　analysis　was　conducted　to　manipulate　the　equilibrium　and　correlate　with　the　reactivity　of　reactants.　The　structural　features　of　aldehydes　and　secondary　amines　were　identified,　and　both　polar　and　steric　effects　have　significant　impact　on　the　binding.　In　particular,　the　substrates　which　can　participate　in　π-π　and　polar-π　interactions　are　able　to　afford　apparent　equilibrium　constants　in　the　magnitude　of　104　M-2,　demonstrating　the　power　of　weak　supramolecular　forces　to　stabilize　the　dynamic　covalent　assembly.　The　generality　of　the　assembly　was　validated　with　a　series　of　mono　secondary　alcohols.　To　showcase　the　practicality　of　our　system,　chirality　discrimination　and　ee　measurement　of　chiral　secondary　alcohols　were　achieved.　©　2015　American　Chemical　Society.