Diagnosis of GERD is frequently done based on the symptoms and often physicians put the patients on a therapeutic trial of antacids. But it must be remembered that patients responding positively to therapeutic trial of antacids do not always have GERD; they may well be suffering from some other condition (Gastric ulcer, duodenal ulcer, etc). Hence it's very important to evaluate every case of heartburn to diagnose if it's due to GERD or due to any other cause.
Following are the commonest investigations done to diagnose GERD:
Upper Gastrointestinal Endoscopy: Also commonly known as OGD scopy or Oesophago-gastro-duodenoscopy (endoscopy of the upper digestive tract). This involves viewing the inside of the food pipe, stomach and upper part of intestine using a fibre-optic tube to look out for any inflammation, erosions, ulcers and to rule out any complications of GERD.
Biopsy of the esophagus is more important for ruling out cancer of the esophagus or other cellular changes as a cause of heartburn. A biopsy can also pick up other cellular changes that may be complications of GERD.
Specialised x-ray of the esophagus (called esophagram) using barium as contrast: This is done to rule out complications of GERD such as ulcers, strictures, etc. This test is not used frequently nowadays and Endoscopy remains the primary diagnostic test.
Esophageal motility testing: To evaluate the function of the muscles of the esophagus.
Gastric emptying studies: To detect if the patient has slow emptying of the stomach.
Esophageal acid testing: To determine the amount of time during 24 hours that the esophagus contains acid.
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Diagnosis 
