Background: In a rapidly digitalizing world, the inability of older adults to leverage digital technology has been associated with weaker social connections and poorer health outcomes. Despite the widespread digital adoption in Singapore, older adults, especially those of lower socioeconomic status (SES), still face difficulties in adopting information and communications technology and are typically digitally excluded. Objective: We aimed to examine the impact of the volunteer-led, one-on-one, and home-based digital literacy program on digital literacy and health-related outcomes such as self-reported loneliness, social connectedness, quality of life, and well-being for older adults of low SES. Methods: A nonrandomized controlled study was carried out in Singapore between July 2020 and November 2021 involving 138 digitally excluded community-dwelling older adults aged ≥55 years and of lower SES. Older adults awaiting participation in the program served as controls. Older adults under the intervention were equipped with a smartphone and cellular data, underwent fortnightly to monthly digital literacy training with volunteers to learn digital skills, and digitally connected to their existing social networks. Primary outcome was the improvement in self-reported digital literacy. Secondary outcomes included improvements in University of California, Los Angeles 3-item loneliness scale, Lubben Social Network Scale-6, EQ-5D-3L and EQ visual analogue scale scores, and Personal Wellbeing Score. Results: There were significant improvements in digital literacy scores in the intervention group as compared to controls (mean difference 2.28, 95% CI 1.37-3.20; P<.001). Through multiple linear regression analyses, this difference in digital literacy scores remained independently associated with group membership after adjusting for differences in baseline scores, age, gender, education, living arrangement, housing type, and baseline social connectivity and loneliness status. There was no statistically significant difference in University of California, Los Angeles 3-item loneliness scale, Lubben Social Network Scale-6, Personal Wellbeing Score, or EQ-5D Utility and visual analogue scale score. Conclusions: This study adds to the growing research on digital inclusion by showing that a volunteer-led, one-on-one, and home-based digital literacy program contributed to increase digital literacy in older adults of low SES. Future studies should look into developing more older adult–friendly digital spaces and technology design to encourage continued digital adoption in older adults and, eventually, impact health-related outcomes.