Many investigations have been devoted to mechanical resistance and other general properties of plastic pipes as required by technical standards. However, very few research studies have been involved with internal and external pipe surface qualities in relation to aggressive chemical agents. The aim of this work is to present the effects of an equimolar toluene methanol (TM) mixture on mechanical and morphological properties of HDPE-100 pipe surfaces (or layers). Using optimum machining conditions, four different specimen geometries, representative of either surfaces or layers, are manufactured and subsequently aged in TM environment. Laboratory sorption experiments for inner (IL) and outer (OL) pipe layers show that equilibrium is attained within 4 days. Stress-strain tests indicate that outer and inner pipe envelopes, once separated, behave as if they were dissimilar pipes. Indeed, for the as-received pipe IL, the properties E, σy, σf, and ef exceeded those of the OL by 50%, 11%, 9%, and 6%, respectively. After 7-day exposure to TM mixture, the same trend is conserved with somewhat lower values. Most of filament properties are also in favor of the IL after 1290 days in TM mixture. It is found that E dropped significantly compared to the as-received material (OL = − 35% and IL = − 43%) while ef for OL is cut by almost two thirds. The outer surface is rougher than the inner one due to interaction with the extrusion die. As a result, the TM mixture generally causes PE swelling and narrows the gap between roughness (Rz) values with a more pronounced effect for the external surface. The value of Rz dropped from 7.15 to 2.80 μm after 1290 days, whereas the internal surface showed a slight increase up to 7%. This is explained by the particularities of the extrusion process which cools the external surface rapidly giving rise to different morphologies in pipe layers associated to the plasticizing effect of the solvent. Structural changes imparted by extrusion and TM ageing are characterized via crystallinity and oxidation induction time (OIT). It is concluded that after 1290 days, crystallinity and OIT decreased for IL and OL because of structure degradation such as anti-oxidant depletion and pigment loss. Interestingly, it is concluded that crystallinity evolution coincides with OIT progression according to lifetime and to position crosswise pipe wall.