The surface pretreatment of a Ti substrate to produce metal oxide electrodes with electrocatalytic properties is of fundamental importance. The preparation of the substrate prior to the application of the coating critically affects the properties of the coating, including its surface roughness, adhesion, and corrosion resistance. In this work, different treatments were applied to the surfaces of Ti discs and their effects on surface roughness were studied. The treatments applied to Ti consisted of three stages: (1) mechanical treatment, (2) degreasing, and (3) chemical treatment. The first stage was carried out with 120 grit SiC abrasive sandpaper, the second stage was carried out with acetone (group A) or sodium hydroxide (NaOH) solution (group B), and the third stage was conducted using hydrochloric acid (HCl), oxalic acid, a mixture of hydrofluoric acid (HF)/phosphoric acid (H3PO4), or a sequence of all three chemical treatments (i.e., HCl, oxalic acid, and HF/H3PO4). The morphological properties, surface composition, and electrochemical behavior of the treated Ti discs were characterized by scanning electron microscopy (SEM), X-ray diffractometry (XRD) and cyclic voltammetry (CV) in a 0.5 M H2SO4 solution, respectively. The electroactive surface area (Aes) and roughness factor (frs) of each Ti disc were estimated from capacitance measurements of the electrochemical double layer. The morphology and voltammetric behavior of Ti varied markedly depending on the surface treatment applied. In addition, the XRD results showed that Ti surfaces subjected to different treatments exhibited different crystallographic planes. The trend in surface roughness with respect to the chemical reagent used was as follows: Group A: oxalic acid > HF/H3PO4 > global treatment > acetone > HCl; Group B: oxalic acid > HF/H3PO4 > NaOH > HCl > global treatment. The most severe chemical attack on the substrate was induced by oxalic acid, which led to the largest electroactive area and roughness factor among the treated Ti samples investigated in this study.