How to add custom file before toolbar section in category listing page ?

Step 1: Create local.xml file in your current theme folder.
          app/design/frontend/[Vendor]/[Theme]/layout/local.xml

Step 2: Add Below code.

// When Layered Navigation is enable
    <catalog_category_layered>
<reference name="content">
<block type="core/template" name="custom_file" as="custom_file" template="catalog/product/custom.phtml" before="product_list_toolbar" />
</reference>
    </catalog_category_layered>

    <catalog_category_default>
<reference name="content">
<block type="core/template" name="custom_file" as="custom_file" template="catalog/product/custom.phtml" before="product_list_toolbar" />
</reference>
    </catalog_category_default>

Step 3: Add custom.phtml file in app/design/frontend/[Vendor]/[Theme]/template/catalog/product folder.