The drug Avastin should not be used to treat secondary breast cancers, the NHS drugs advisory body NICE says.
The National Institute for Health and Clinical Excellence, which issues guidance for NHS in England and Wales, said there was insufficient evidence that the drug prolonged life.
Cancer charities say the decision is disappointing.
Avastin, also known as bevacizumab, works by starving cancer cells of a blood supply.
It is designed to be used in conjunction with another chemotherapy drug, paclitaxel. Clinical trials in breast cancer patients suggested that it might slow the growth and spread of tumours by five months more than using paclitaxel alone.
The National Institute for Health and Clinical Excellence said there were uncertainties in the evidence and that it was unable to confirm whether the drug could extend a patient's life or improve quality of life.
Sir Andrew Dillon, chief executive of NICE, said: "The evidence for the effectiveness of bevacizumab in prolonging survival was not robust and overall did not show enough of a demonstrable benefit for it to be considered a cost-effective use of NHS resources.
"NICE is committed to ensuring the most effective and efficient treatments. We already recommend a range of treatment options for patients with metastatic breast cancer in our clinical guideline for advanced breast cancer."
Dr Emma Pennery, clinical director at Breast Cancer Care said: "This recommendation will be disappointing for people with secondary breast cancer.
"In the mean time, doctors who believe their patients could benefit from bevacizumab can apply for funding through the Cancer Drugs Fund and we encourage people to discuss this option."
Meg McArthur, senior policy officer at Breakthrough Breast Cancer, said: "We are disappointed with NICE's final decision not to approve Avastin with a taxane. However, as a treatment for metastatic breast cancer, it would not be appropriate for everyone and so we encourage continued investment into effective treatment options.
"We follow with interest new initiatives, including the Cancer Drugs Fund, which could improve access to drugs for cancer patients."