Titanium tubes generally exhibit superior resistance against electrochemical corrosions amid seawater for their passive films TiO2. However, hydrogen-assisted corrosion (HAC) is actually the Achilles' heel to titanium materials when the temperature exceeds near 70 °C. In this event, severe degradations like quick thinning and leakage were frequently detected on a large number of titanium tubes exposed to natural seawater environment within heat exchangers in a nuclear power plant, which caused serious safety problems. This paper is the Part I of totally two parts conducted for the whole failure analysis study, mainly focusing on electrochemical aspect of failure causes and their behaviors. By means of over ten kinds of characterization methods, the analysis results identified that the HAC induced by the interaction effects between galvanic corrosion and crevice corrosion led to local bulges of the inner walls of some titanium tubes, and then the bulges were quickly thinned and eventually ruptured under the eddy erosion from the seawater containing sediment particles. Finally, relevant mechanisms were addressed in detail and prevention methods were proposed as well.