Meso-tetraphenylporphyrinatooxidovanadium(IV) [VIVO(TPP)] (1) and 2,3,7,8,12,13, 17,18-octabromo-meso-tetraphenylporphyrinatooxidovanadium(IV) [VIVO(TPPBr8)8)] (2) were synthesized and characterized by various spectroscopic techniques. 1 and 2 were utilized as efficient catalysts for the selective epoxidation of olefins. Catalyst 2 shows very high catalytic activity (TOF = 8783–13108 h−1)−1) as compared to 1 (TOF = 2175–3296 h−1)−1). The catalysts are recyclable, as their recyclability was checked for four cycles and show only minor reduction of their efficiency.