The purpose of this study is to explore the undergraduates’ perception of the quality and value of library services offered to them in the 21st-century in federal universities in Southeast Nigeria. Prof. Festus Aghagbo Nwako Library (PFANL) in Nnamdi Azikiwe University Awka was used as a case study. A descriptive survey research design was adopted for the study. From a population of 14,196 registered regular undergraduates’ users of the library, a sample of 120 was selected through an accidental sampling technique. From 120 questionnaires distributed, 103 copies received were valid, 17 responses were either incomplete or not answered, and so, the efficient rate was 85.8 percent. The study employed the use of two instruments which include: observation checklist, used to ascertain the available library services, and a questionnaire used to elicit users’ perception of library service quality and value. The instruments were face validated by two experts in Nnamdi Azikiwe University Awka. The internal consistency of the instrument on library services used by the undergraduates was established using Kudder-Richardson which yielded 0.86 while Cronbach's alpha coefficient was used for the undergraduates’ perception of quality and value of library services offered to them which yielded 0.78 and 0.81 respectively. Frequency count, percentage, mean and standard deviation using SPSS, were used to analyze data from research questions, t-test was used to test hypotheses. The major findings revealed that the undergraduates have a positive perception of the quality of library services offered to them at Prof. Festus Aghagbo Nwako Library (PFANL). However, they had a negative perception of the quality of computer/Internet services and reprographic services offered to them. This shows that these two services should immensely be improved upon in this 21st-century. The study equally shows that undergraduates have high value for library services offered to them. Nevertheless, they have low value on computer/internet services and reprographic services which are most needed in this 21st-century. The finding also revealed the host of impediments that affects high perception of library services quality and value in this 21st century at PFANL to include; insufficient current information resources, an unfriendly attitude of staff, slow internet connectivity, limited access, insufficient availability of modern facilities, insufficient training on technology use and unsteady power supply. The finding further revealed that there is no significant difference in mean rating of male and female perception of quality and value of library service offered to them at PFANL. Based on the findings, it was recommended among others that the library management at PFANL should sustain undergraduates’ level of perceived library quality and value, and boost it by providing continuously, relevant and current information resources and services especially on the aspect of computer/Internet services and reprographic services suitable in this 21st-century.