Recent studies have revealed the prognostic role of the gamma gap, the total serum proteins concentration minus the albumin concentration, for predicting all-cause mortality among adults. This study aims to investigate the relationship between the gamma gap and all-cause mortality among nonagenarians and centenarians via a secondary data analysis of a prospective observational study. The analysis included 801 participants (260 men and 541 women, mean age: 93.7 ± 3.5 years), 46 of which were lost at the 4-year follow-up. The mean gamma gap was 2.7 ± 0.5 g/dl. After adjusting for relevant confounders, the gamma gap was significantly associated with 4-year all-cause mortality (hazard ratio [HR] per 1-SD = 1.22, 95% confidential interval [CI]: 1.12-1.78). Using different cut-off points, the elevated gamma gap could be defined as ≥2.9, 3.0, 3.1, or 3.2 g/dl. The relevant HRs and 95% CIs of the elevated gamma gap for predicting mortality were 1.27 (1.12-1.90), 1.29 (1.03-1.78), 1.21 (1.23-1.66), and 1.26 (1.09-1.69), respectively. In conclusion, the gamma gap is an independent prognostic factor for long-term mortality in nonagenarians and centenarians. A value greater than or equal to 3.1 g/dl may define an elevated gamma gap, but further studies are required.