Sedentary behaviors are an important issue worldwide, as prolonged sitting time has been associated with health problems. Recently, active workstations have been developed as a strategy to counteract sedentary behaviors. The present study examined the rationale and perceptions of university students’ and staff following their first use of an active workstation in library settings. Ninety-nine volunteers completed a self-administered questionnaire after using a portable pedal exercise machine (PPEM) or a standing desk (SD). Computer tasks were performed on the SD (p = 0.001) and paperwork tasks on a PPEM (p = 0.037) to a larger extent. Men preferred the SD and women chose the PPEM (p = 0.037). The appreciation of the PPEM was revealed to be higher than for the SD, due to its higher scores for effective, useful, functional, convenient, and comfortable dimensions. Younger participants (<25 years of age) found the active workstation more pleasant to use than older participants, and participants who spent between 4 to 8 h per day in a seated position found active workstations were more effective and convenient than participants sitting fewer than 4 h per day. The results of this study are a preliminary step to better understanding the feasibility and acceptability of active workstations on university campuses.