Hydrophilization of Polyamide 46 (PA46) via modification with acetaldehyde in continuous phase was studied. The chemical modification of PA 46 with acetaldehyde resulted in a water-swollen polymer with hydrophilic property. The polyamide 46 undergoes a nucleophilic addition with acetaldehyde in the presence of aluminum chloride as a catalyst. The extent of bulk hydroxyethylation using AlCl3 resulted in 95.65% modification counted as total N-hydroxyethylated polyamide 46. The modification resulted in improved hydrophilic properties, and a maximum surface free energy of 44.6 mJ/m2 was achieved after 3 h reaction, whereas the unmodified PA46 had a surface free energy of 11.2 mJ/m2. In addition, thermal properties of the polymers were studied using differential scanning calorimetry and thermogravimetric analyses. The functionalization leads to decrease in the crystallization energy from 88 J/g to 51 J/g, while the melting energy is changed from 110 J/g to 53 J/g. Furthermore, the thermal stability of the PA46 to pyrolysis was diminished after hydroxylation.