While telemedicine services enjoy a high acceptance among the public, evidence regarding clinician’s acceptance, a key factor for sustainable telemedicine services, is mixed. However, telemedicine is generally better accepted by both patients and professionals who live in rural areas, as it can save them significant time. The objective of this study is to assess the acceptance of medical record-based, store and forward provider-to-provider telemedicine among primary care professionals and to describe the factors which may determine their future use. This is an observational cross-sectional study using the Catalan version of the Health Optimum questionnaire; a technology acceptance model-based validated survey comprised of eight short questions. The online, voluntary response poll was sent to all 661 primary care professionals in 17 primary care teams that had potentially used the telemedicine services of the main primary care provider in Catalonia, in the Central Catalan Region. The majority of respondents rated the quality of telemedicine consultations as “Excellent” or “Good” (83%). However, nearly 60% stated that they sometimes had technical, organizational or other difficulties, which might affect the quality of care delivered. These negatively predicted their declared future use (p = 0.001). The quality of telemedicine services is perceived as good overall for all the parameters studied, especially among nurses. It is important that policymakers examine and provide solutions for the technical and organizational difficulties detected (e.g., by providing training), in order to ensure the use of these services in the future.