We present 22901 OB spectra of 16032 stars identified from the Large Sky Area Multi-Object Fiber Spectroscopic Telescope data release 5 (LAMOST DR5) data set. A larger sample of OB candidates are first selected from the distributions in the spectral line indices' space. Then, all 22901 OB spectra are identified by manual inspection. Based on a subsample validation, we find that the completeness of the OB spectra reaches about 89+/-22% for the stars with spectral types earlier than B7, while around 57+/-16% B8-B9 stars are identified. The smaller completeness for late B stars will lead to the difficulty in discriminating them from A0-A1-type stars. The subclasses of the OB samples are determined using the software package MKCLASS. With a careful validation using 646 subsamples, we find that MKCLASS can give fairly reliable subtypes and luminosity classes for most of the OB stars. The uncertainty of the spectral subtype is around 1 subtype, and the uncertainty of the luminosity class is around 1 level. However, about 40% of the OB stars fail to be assigned to any class by MKCLASS, and a few spectra are significantly misclassified by MKCLASS. This is likely because the template spectra of MKCLASS are selected from nearby stars in the solar neighborhood, while the OB stars in this work are mostly located in the outer disk and may have lower metallicities. The rotation of the OB stars may also be responsible for the misclassifications. Moreover, we find that the spectral and luminosity classes of the OB stars located in the Galactic latitude larger than 20{deg} are substantially different with those located in the latitude smaller than 20{deg}, which may either be due to the observational selection effect or may hint a different origin of the high Galactic latitude OB stars.