This study experimentally investigated the effects of nanomaterials and interface fiber angle on the mode I fracture toughness of woven carbon fiber-reinforced polymer (CFRP) composites. Three different types of nanomaterials were used: COOH-functionalized short multi-walled carbon nanotubes (S-MWCNT-COOH), multi-walled carbon nanotubes (MWCNTs), and graphene nanoplatelets (GnPs). Double cantilever beam specimens were composed of 12 woven carbon fiber fabrics with/without 1 wt% nanomaterials, and were manufactured using the hand lay-up method. Furthermore, two different stacking sequence series were used; the first series comprised only on-axis carbon-fiber fabrics (0° or 90°), and the second series comprised both on- and off-axis carbon-fiber fabrics (0° or 90° and ±45°). The test results showed that adding S-MWCNT-COOH, MWCNTs, and GnPs significantly increased the mode I fracture toughness of the CFRP composites for both the stacking sequence series. Moreover, the specimens that used only on-axis carbon fiber fabrics exhibited higher fracture toughness values than those of the specimens that used on- and off-axis carbon fiber fabrics together. In addition, an empirical model was established to predict the fracture toughness of the CFRP composites with nanomaterials by using on- and off-axis carbon fiber fabrics together, and the prediction results showed a good agreement with the experimental results.