The recently emerging vinylene-linked covalent organic frameworks (VCOFs) stand out from other COFs with exceptional chemical stability and favorable light-emitting properties, promising sensing applications for acids/bases or in strong acidic/basic conditions. Here we systematically investigated the reversible color and fluorescent response of a VCOF functionalized with pyridyl groups to acids/pH. The COF was synthesized with a record surface area for VCOFs and shows reversible hydrochromic and acidochromic behaviors and concomitant fluorescence quenching. The mechanisms were probed with systematical experimental comparison with relevant COFs and model molecules in combination with orbital analysis. The response is related to significant electronic changes in the ground and photoexcited states as a result of protonation or hydrogen bonding at pyridyl sites. The COF in aqueous dispersion displays a reversible fluorescence transition with pH change, which follows the Hill equation for multisite protonation. The COF-modified test paper shows immediate and remarkable color change and fluorescence turn-off/on when alternately exposed to HCl and NH3 gases. The work illustrates the great potential of developing highly robust sensory COFs through the vinylene approach.