Charlotte Brontë’s visually detailed character descriptions illustrate her participation in the Victorian fascination with the legibility of the inner self. Although much has been said about her use of visual imagery to evoke interiority, critics have not yet addressed her treatment of dress as a signifier. This dissertation examines Brontë’s use of clothing in characterization, particularly how it engages the Victorian discourses of physiognomy and phrenology. In her writing she frequently employs these culturally accepted pseudo-sciences, which posit that the face and the skull offer clues to identity. These taxonomies presume that character is more or less fixed according to one’s physical features. This dissertation demonstrates how Brontë uses dress in order to subvert the pseudo-sciences’ notion that the body houses a relatively stable, unitary self. Over time, she shifts her attention from the coded face to clothing as a more suitable means of representing subjectivity since it better expresses the performative aspect of identity. The emergence of the plain heroine in the juvenilia and published novels contributes to this shift; her contradictory facial features and distinctly unfashionable mode of dress index her process of self-development. The first chapter addresses the influence of the silver-fork school on her early character descriptions and the first appearance of the plain heroine in the juvenilia. The second chapter demonstrates how, in Jane Eyre, the protagonist manages contradictory elements of her character by dressing plainly, and the third explores how, in Villette, Lucy Snowe extends the boundaries of her identity by wearing unlikely costumes. By investing materialist pseudo-science and material garments with psychological meaning, Brontë achieves an unprecedented representation of women’s interior lives in nineteenth-century fiction.