The higher-order asymptotic properties provide better approximation of the bias for a class of estimators. The first-order asymptotic properties of the asymmetric least squares (ALS) estimator have been investigated by Newey and Powell (Econometrica55, 4, 819-847 1987). This paper develops the second-order asymptotic properties (bias and mean squared error) of the ALS estimator, extending the second-order asymptotic results for the symmetric least squares (LS) estimators of Rilstone et al. (J. Econometr.75, 369-395 1996). The LS gives the mean regression function while the ALS gives the "expectile" regression function, a generalization of the usual regression function. The second-order bias result enables an improved bias correction and thus an improved ALS estimation in finite sample. In particular, we show that the second-order bias is much larger as the asymmetry is stronger, and therefore the benefit of the second-order bias correction is greater when we are interested in extreme expectiles which are used as a risk measure in financial economics. The higher-order MSE result for the ALS estimation also enables us to better understand the sources of estimation uncertainty. The Monte Carlo simulation confirms the benefits of the second-order asymptotic theory and indicates that the second-order bias is larger at the extreme low and high expectiles.