Three new procyanidins (<b>1</b>-<b>3</b>), two new phlobatannins (<b>6</b> and <b>7</b>), a new flavan-3,4-diol glycoside (<b>9</b>), and a new neolignan glycoside (<b>10</b>), along with three previously reported compounds (<b>4</b>, <b>5</b>, and <b>8</b>) were isolated from the twigs of <i>Rosa multiflora</i>. The chemical structures of the new compounds (<b>1</b>-<b>3</b>, <b>6</b>, <b>7</b>, <b>9</b>, and <b>10</b>) were characterized by spectroscopic data interpretation, including NMR (<sup>1</sup>H and <sup>13</sup>C NMR, <sup>1</sup>H-<sup>1</sup>H COSY, HSQC, HMBC, and NOESY) and HRESIMS analysis. Experimental ECD data analysis was conducted to assign the absolute configurations of the new compounds (<b>1</b>-<b>3</b>, <b>6</b>, <b>7</b>, <b>9</b>, and <b>10</b>). The absolute configuration of the sugar moieties was verified through a chiral derivatization method and LC-MS analysis. All the isolated compounds (<b>1</b>-<b>10</b>) were evaluated for their anti-neuroinflammatory activity based on inhibitory effects on nitric oxide production using a lipopolysaccharide-stimulated murine microglia BV-2 cell line and for their neurotrophic effects on nerve growth factor induction in C6 glioma.