Peripheral intravenous catheterization (PIVC) is frequently required for various medical treatments. Over 1 billion PIVC operations are performed per year in the United States alone. However, this operation is characterized by a very low success rate, especially amongst pediatric patients. Statistics show that only 53% of first PIVC attempts are successful in pediatric patients. Since their veins are small and readily rupture, multiple attempts are commonly required before successfully inserting the catheter into the vein. This article presents and evaluates a novel venous entry detection method based on measuring the electrical bio-impedance of the contacting tissue at the tip of a concentric electrode needle (CEN). This detection method is then implemented in the design of a clinical device called smart venous entry indicator (SVEI), which lights up a LED to indicate the venous entry when the measured value is within the range of blood. To verify this detection method, two experiments are conducted. In the first experiment, we measured the bio-impedance during the insertion of a CEN into a rat's tail vein with different excitation frequencies. Then three classifiers are tested to discriminate blood from surrounding tissues. The experimental results indicate that with 100 kHz excitation frequency the blood bio-impedance can be identified with accuracy nearly 100%, demonstrating the feasibility and reliability of the proposed method for venous entry detection. The second experiment aims to assess the impact of SVEI on PIVC performance. Ten naive subjects were invited to catheterize a realistic baby arm phantom. The subjects are equally divided into two groups, where one group does PIVC with SVEI and the other group uses an ordinary IV catheter. The results show that subjects using SVEI can achieve much higher success rates (86%) than those performing PIVC in a conventional way (12%). Also, all subjects assisted by SVEI succeeded in their first trials while no one succeed in their first attempt using the conventional unassisted system. These results demonstrate the proposed detection method has great potential to improve pediatric PIVC performance, especially for non-expert clinicians. This supports further investment towards clinical validation of the technology.