Background: Radial artery (RA) catheterization for invasive blood pressure monitoring is often performed via palpation, and an ultrasound is used secondarily only in case of multiple unsuccessful attempts. Although more elaborate, it has been shown that primary ultrasound-guided catheterization may be advantageous compared with palpation. The aim of this study was to identify factors associated with difficult RA catheterization. Methods: Left RA ultrasound assessments were performed in patients with indicated invasive blood pressure monitoring the day before surgery. RA catheterization was performed by personnel blinded to the ultrasound results. Based on the number of attempts needed for successful catheter placement, the cohort was divided into uncomplicated (group 1) and difficult (more than one attempt, group 2) catheterization cases. Cases subjected to primary ultrasound were excluded from the analysis. Results: Body weight, height and surface area (BSA) of patients in group 2 (n = 16) were significantly lower than those of patients in group 1 (n = 25), and internal RA diameters were significantly smaller in group 2 patients. In the whole cohort, BSA was significantly associated with distal and proximal internal RA diameters. In contrast, no differences were observed in the skin-to-artery distance, the longitudinal axis deviation (kinking) or blood flow velocity. Median time to successful catheterization was 77 (47–179) s. Prolonged time needed for cannulation was significantly associated with lower body weight, BMI and BSA, and with reduced distal and proximal internal RA diameter. Conclusions: RA catheterization performed through pulse palpation may be difficult, especially in adult patients with lower body weight and height, due to reduced arterial diameters. Initial use of ultrasound in these patients may reduce first-attempt failure, preventing procedural delays and patient discomfort.