This article presents the first application of gold nanoparticles deposited capillaries as pre-concentration devices for in-capillary microextraction CZE and their use for the analysis of monohydroxy-polycyclic aromatic hydrocarbons in synthetic urine samples. The successful separation of 1-hydroxypyrene, 9-hydroxyphenanthrene, 3-hydroxybenzo[a] pyrene (3-OHbap), 4-hydroxybenzo[a] pyrene and 5-hydroxybenzo[a] pyrene under a single set of electrophoretic conditions is demonstrated as well as the feasibility to obtain competitive ultraviolet absorption LOD with commercial instrumentation. Enrichment factors ranging from 87 (9-OHphe) to 100 (3-OHbap) made it possible to obtain LOD ranging from 9 ng/mL (9-OHphe and 3-OHbap) to 14 ng/mL (4-hydroxybenzo[a] pyrene).