Using the structural and electronic tunability of molecules to control magnetism is a central challenge of inorganic chemistry. Herein, a ten-member family of the high-ordering temperature (T_c) molecule-based magnetic coordination networks of the form V[x-Cl_nPTCE]₂·yCH₂Cl₂ (PTCE = phenyltricyanoethylene, y < 0.5) were synthesized and characterized, where x is (are) the position(s) and n is the number of chlorine substitutions on the phenyl ring. These chlorophenyltricyanoethelenes are tunable analogs of the more commonly investigated tetracyanoethylene (TCNE). Varying the number and position of chlorine substitution around the phenyl ring engendered a family of network solids with significantly different magnetic ordering temperatures ranging from 146 to 285 K. The T_cs of these ferrimagnets were rationalized with the aid of cyclic voltammetry and Density Functional Theory (DFT) calculations.