Constructing multiple functional geometric frustration magnets is a hot topic in solid state chemistry and material science. Herein, a two‐dimensional (2D) parallel interpenetrating "star" net complex [HDMPDA][Fe6(μ3‐O)2(μ‐O2CH)15] (1) was obtained successfully with HDMPDA (DMPDA=N, N'‐dimethyl‐1,3‐propanediamine) as charge balancer. The dipole reorientation of the rotator [HDMPDA] in the complex brings a structure transition which leads dielectric relaxation close to room temperature. Despite strong antiferromagnetic coupling existing between ions in the net, long‐range order temperature TN of the complex is suppressed to 4.2 K by geometric frustration. Interestingly, below TN, a canted antiferromagnetic state, accompanied with slow magnetic relaxation, is detected due to the lack of enough magnetic coupling between 2D layers. Thus, 1 is a particular multifunctional magnetic frustration material containing two different types of relaxations.