A novel unsymmetrical diamine, 1,3-bis(4-aminophenoxy)naphthalene, was prepared through the nucleophilic displacement of 1,3-dihydroxynaphthalene with p-fluoronitrobenzene in the presence of potassium carbonate, followed by catalytic reduction with hydrazine. A series of novel aromatic polyimides containing bis(phenoxy)naphthalene units were synthesized from the unsymmetrical diamine and a range of aromatic tetra-carboxylic dianhydrides via the usual two-step procedures that included ring-opening polyaddition and thermal/chemical cyclodehydration. The poly(amic acid)s had inherent viscosities ranging from 0.65 to 2.01 dL/g. All the poly(amic acid)s could be converted thermally into transparent, flexible, and tough polyimide films. Most of the polyimides were soluble in organic solvents, such as dimethylacetamide, N-methyl-2-pyrrolidone, m-cresol, or o-chlorophenol due to the unsymmetrical and bulky pendant naphthalene groups. The tensile strength and elongation at break of the polyimide films ranged from 74 to 97 MPa and 4 to 7%, respectively. These polyimides had glass transition temperatures ranging from 221 to $312^{circ}C$. Thermogravimetric analysis revealed these polymers to be fairly stable up to $500^{circ}C$, and the 10% weight loss temperature were recorded in the range of $531-580^{circ}C$ in nitrogen and $522-570^{circ}C$ in air. The substituted position effect of bis(phenoxy)naphthalene on the properties of the polyimides were investigated. The polyimides derived from unsymmetrical 1,3-substituted bis(4-aminophenoxy) naphthalene showed better solubility without sacrificing their thermal and mechanical properties due to the unsymmetrical and bulky pendant effects.