Chitosan and pectin form complexes owing to electrostatic interactions between positively charged amino groups in chitosan and negatively charged carboxylate groups in pectin, which was confirmed by ATR‐FTIR spectroscopy and contact angle measurements. Moreover, the formation of these complexes might be associated with the loss of the biopolymers ordering, which resulted in higher surface roughness and lower thermal stability of the complexes in comparison to those of homopolymers.UV rays, used as a sterilizing agent, caused a moderate increase in the surface polarity of the complexes. Roughness parameters of these samples changed irregularly after irradiation, and their thermal stability was slightly affected by UV rays. The results indicated that the complexes studied appeared to present resistance to UV action higher than homopolymers, which is a desirable property in medical or pharmaceutical applications.