Preheat oven to 375°.
To prepare cake, coat a 10-inch tube pan with cooking spray; dust with 2 tablespoons flour. Set aside.
Place sugar and eggs in a large bowl; beat with a mixer at medium speed until thick and pale (about 3 minutes).
Lightly spoon 3 cups flour into dry measuring cups; level with a knife. Combine flour, baking powder, aniseed, salt, and cinnamon, stirring well with a whisk.
Combine rind, 1/2 cup juice, oil, and vanilla. Add flour mixture to egg mixture alternately with juice mixture, beginning and ending with flour mixture; blend after each addition just until combined. Stir in pear and walnuts. Pour batter into prepared pan. Bake at 375° for 55 minutes or until a wooden pick inserted in center comes out clean. Cool in pan on a wire rack 15 minutes; loosen cake from sides of pan using a narrow metal spatula or knife. Place a plate upside down on top of cake pan; carefully invert cake onto plate.
To prepare syrup, combine honey and 2 tablespoons juice in a small saucepan over medium heat. Cook 2 minutes, stirring constantly. Brush warm syrup over top and sides of cake. Cool completely.