Background: Adjusted clinical groups (ACG®) have been widely used to adjust resource distribution; however, the relationship with effectiveness has been questioned. The purpose of the study was to measure the relationship between efficiency assessed by ACG® and a clinical effectiveness indicator in adults attended in Primary Health Care Centres (PHCs). Methods: Research design: cross-sectional study. Subjects: 196, 593 patients aged >14 years in 13 PHCs in Catalonia (Spain). Measures: Age, sex, PHC, basic care team (BCT), visits, episodes (diagnoses), and total direct costs of PHC care and co-morbidity as measured by ACG® indicators: Efficiency indices for costs, visits, and episodes (costs EI, visits EI, episodes EI); a complexity or risk index (RI); and effectiveness measured by a general synthetic index (SI). The relationship between EI, RI, and SI in each PHC and BCT was measured by multiple correlation coefficients (r). Results: In total, 56 of the 106 defined ACG® were present in the study population, with five corresponding to 44.5% of the patients, 11 to 68.0% of patients, and 30 present in less than 0.5% of the sample. The RI in each PHC ranged from 0.9 to 1.1. Costs, visits, and episodes had similar trends for efficiency in six PHCs. There was moderate correlation between costs EI and visits EI (r = 0.59). SI correlation with episodes EI and costs EI was moderate (r = 0.48 and r = −0.34, respectively) and was r = −0.14 for visits EI. Correlation between RI and SI was r = 0.29. Conclusions: The Efficiency and Effectiveness ACG® indicators permit a comparison of primary care processes between PHCs. Acceptable correlation exists between effectiveness and indicators of efficiency in episodes and costs.