Merging behavior is inevitable at on-ramp bottlenecks and is a significant factor in triggering traffic breakdown. In modeling merging behaviors, the gap acceptance theory is generally used. Gap acceptance theory holds that when a gap is larger than the critical gap, the vehicle will merge into the mainline. In this study, however, analyses not only focus on the accepted gaps, but also take the rejected gaps into account, and the impact on merging behavior with multi-rejected (more than once rejecting behavior) gaps was investigated; it shows that the multi-rejected gaps have a great influence on the estimation of critical gap and merging prediction. Two empirical trajectory data sets were collected and analyzed: one at Yan’an Expressway in Shanghai, China, and the other at Highway 101 in Los Angeles, USA. The study made three main contributions. First, it gives the quantitative measurement of the rejected gap which is also a detailed description of non-merging event and investigated the characteristics of the multi-rejected gaps; second, taking the multi-rejected gaps into consideration, it further expanded the concept of the “critical gap” which can be a statistic one and the distribution function of merging probability with respect to such gaps was analyzed by means of survival analysis. This way could make the full use of multi-rejected gaps and accepted gaps and reduce the sample bias, thus estimating the critical gap accurately; finally, considering multi-rejected gaps, it created logistic regression models to predict merging behavior. These models were tested using field data, and satisfactory performances were obtained.