AbstractThe technique of nitric acid etching followed by gel permeation chromatography (GPC) has been used to study the structure of ultrahigh‐modulus linear polyethylene (LPE) tapes drawn to draw ratio λ of 20. For comparison, lower draw ratio (λ = 11) samples were also examined. The etching was carried out in fuming nitric acid at 60°C and the progress of the reaction was monitored by measuring weight loss and molecular weight distributions as a function of time over a period up to 25 days. Consistent with previous work by us and other workers, notably Porter and Peterlin and co‐workers, the ultrahigh‐modulus products exhibit an exceptional resistance to the acid attack, i.e., after 3 days their weight loss is still negligible while at lower draw ratios it could be as high as 30%. At longer times, however, the rate of weight loss becomes comparable for the two sets of samples, even if the absolute values are much smaller for the products of λ = 20. During the early stages of the etching treatment a rapid decrease in molecular weight and narrowing of the molecular weight distribution is observed in all cases. Eventually the molecular weight distribution becomes time independent, while the weight loss continues to increase. This stage coincides with the attack of the lateral surfaces of the crystals becoming the dominant process and it is considered that the observed molecular length distribution then reflects the distribution of crystal thicknesses. The values of the weight average crystal thickness derived from the GPC experiments (L̄w) are in very good agreement with those obtained from wide‐angle x‐ray determinations. Furthermore the ratio of weight‐average to number‐average crystal thickness (L̄w/L̄n) is about 2 for the high draw (λ = 20) samples, i.e., the value predicted by the simple statistical model proposed by Gibson, Davies, and Ward for the structure of ultrahigh‐modulus LPE. It is therefore concluded that the nitric acid etching/GPC technique can be used for reliable measurements of crystal size and crystal size distribution in ultraoriented LPE.