Summary: The effect of salts on the conformational behavior of acenaphthylene labeled poly(N,N‐diethylacrylamide) (PDEA/ACE) has been investigated in dilute aqueous solution using UV‐vis and fluorescence spectroscopy. It is demonstrated here that the effectiveness of various salts in changing the lower critical solution temperature (TLCS) of the PDEA/ACE solution followed the Hoffmeister series. The addition of NaCl linearly lowered the TLCS. In dilute aqueous solution, the PDEA/ACE adopted a loose coil conformation below its TLCS. The PDEA/ACE adopted a compact globule conformation above the temperature at which the coil to globule transition (CGT) was completed. A fluorescence anisotropy investigation suggested that a molten globule conformation existed during the CGT of the PDEA/ACE solution. In all of the above three conformations, the PDEA/ACE was more compact in the presence of NaCl than in the absence of any salt.